KR100729970B1 - Image display and method for manufacturing image display - Google Patents

Abstract

In the first invention of the image display device of the present invention, at least one type of particle group or sorting body is enclosed between two opposing substrates transparent, and an electric field is applied to the particle group or sorting body by two kinds of electrodes having different potentials. Is an image display device that displays particles by moving particles or sorting bodies to display an image, wherein an anisotropic conductive film is connected to a member that sends a signal applied to a circuit of image display and a substrate, and a member such as an electrode is transparent It is mounted on the side facing a board | substrate. In the second to sixth inventions of another image display device of the present invention, an electrode is formed on a surface of a substrate with a transparent elastic member interposed therebetween, an antireflection layer is formed, or the bonding of the substrate and the substrate through the partition wall is optimized. have.

Image display

Description

Image display device and manufacturing method of the image display device {IMAGE DISPLAY AND METHOD FOR MANUFACTURING IMAGE DISPLAY}

Field of technology

The present invention relates to an image display apparatus and a method for manufacturing the image display apparatus that can repeatedly display and erase images in accordance with movement of particles or movement of a sorting body by using static electricity such as Coulomb's force. It is about.

Background

Conventionally, as an image display apparatus replacing liquid crystal (LCD), the image display apparatus using techniques, such as an electrophoresis system, an electrochromic system, a thermal system, and a two-color particle rotation system, is proposed.

These conventional technologies are considered as technologies that can be used in the next generation of inexpensive image display devices due to advantages such as a wide viewing angle closer to conventional printed matters, lower power consumption, and a memory function than LCDs. The development of image display for mobile terminals, electronic paper, and the like is expected. In particular, the electrophoretic method which microencapsulates the dispersion liquid which consists of a dispersion particle and a coloring solution, and arrange | positions it between the opposing board | substrates is proposed and the expectation is gathering.

However, in the electrophoresis method, there is a problem in that the response speed is slow due to the viscosity resistance of the liquid because the particles move in the liquid. Moreover, since high-density particles, such as titanium oxide, are disperse | distributed in the low specific gravity solution, it is easy to settle, it is difficult to maintain stability of a dispersed state, and there exists a problem that the image repeat stability is lacking. Even in microencapsulation, the cell size is set at the microcapsule level, so that the above-mentioned defects are not easily seen in appearance, and the essential problem is not solved at all.

On the other hand, with respect to the electrophoretic method using the behavior in the solution, a method of incorporating the conductive particles and the charge transport layer into a part of the substrate without applying a solution is also being proposed (for example, Cho Kuk-rae et al., " New Toner Display Device (I) ", July 21, 1999, Japan Imaging Society Annual Conference (83 times)" Japan Hardcopy'99 ", p.249-252). Because of the arrangement, the structure is complicated and there is also a problem that it is difficult to constantly inject charge into the conductive particles, resulting in lack of stability (a common problem of the first to sixth inventions).

Moreover, when attaching an electrode to an image display apparatus, since the conventional method requires a long time for attaching an electrode, there also exists a problem that manufacturing efficiency of an image display apparatus is low and it adversely affects a board | substrate for heating (1st invention). Challenges).

In addition, when integrated with such a dry display panel and an optical function member having an antireflection function or a touch panel function, a clear image is not obtained when used in an ATM, a CD of a bank, a portable information terminal, a mobile phone, or a computer display. (The subject of 2nd invention).

Further, although it is required to further increase the light transmittance, achieve high contrast, and improve visibility with a clear image, there is a problem that cannot be achieved yet (the problem of the third invention).

In addition, as one method for solving the above-mentioned problems, two or more kinds of particles or sorting bodies having different color and charging characteristics are enclosed between two substrates at least one of which is transparent, and two kinds of electrodes having different potentials BACKGROUND ART Image display apparatuses are known which have an image display panel which imparts an electric field to particles or fractions and moves particles by a coulomb force or the like and moves the fractions to display an image. In this image display device, although the response performance is dry and quick, the structure is simple and inexpensive, and the stability is excellent, since the particle or the classification body is used for image display, the particle or the classification body is interposed between them. There existed a problem that two board | substrates were sealed with an adhesive agent in the state, and the position shift between board | substrates is eliminated and it is hard to prevent the leakage of a particle | grain or a sorting body. For this reason, there also exists a problem that it is difficult to obtain an image display board with high image display precision (a subject of 4th invention).

In addition, in order to solve the above problem, an image display device having a dry response speed, a simple structure, an inexpensive, and excellent stability, having two kinds of different color and charging characteristics between a transparent substrate and an opposing substrate An image display plate having one or more image display elements spaced apart from each other by partition walls for enclosing the particles or the sorting bodies and giving the electric field to the particles or the sorting bodies at two kinds of electrodes having different potentials to move the particles to display the images. There is known an image display device having a structure. In this image display device, an image display element is formed by disposing a partition between a transparent substrate and an opposing substrate.

In the image display apparatus of the above-mentioned structure, conventionally, the partition is arrange | positioned and arrange | positioned the partition between a transparent substrate and an opposing board | substrate, and apply | coated the sealing compound to the edge part of a board | substrate and a partition. Therefore, there is a problem that the bonding between the substrate and the partition wall has a sufficient strength in the case of using a glass substrate as the transparent substrate or the counter substrate, but in the case of using another transparent resin or the like, sufficient bonding strength cannot be obtained. Therefore, the outflow of particles or fractions could not be completely eliminated (a problem of the sixth invention).

Disclosure of the Invention

A first embodiment of the first invention of the present invention relates to a new type of image display device that has been studied in view of the above circumstances, and has a dry response speed, simple structure, low cost, and excellent stability. It is an object to mount an electrode in a short time, and to manufacture the image display apparatus of the outstanding performance efficiently.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, the present inventors enclosed at least 1 type of particle group between two board | substrates which at least one is transparent, and the electric field is carried out to the particle group by the two types of electrodes from which an electric potential differs. As an image display device which moves particles and displays an image by applying the method, an image display device having excellent performance can be efficiently produced by carrying out using an anisotropic conductive film in which conductive particles are dispersed in an adhesive for connection of electrodes. To the present invention.             

That is, the 1st Embodiment of 1st invention of this invention provides the following image display apparatuses.

1. An image display device in which at least one type of particle group is enclosed between two opposing substrates that are transparent, and an electric field is applied to the particle group to move the particles to display an image, which is applied to a circuit of image display. A member which sends a signal is attached to a board | substrate with an anisotropic conductive film, The image display apparatus characterized by the above-mentioned.

2. The said 1 image display apparatus whose average particle diameter of a particle | grain is 0.1-50 micrometers.

3. The image display device of 1 or 2 above, wherein the surface charge density of the particles is 5 to 150 µC / m 2 in absolute value.

4. When the particles apply a voltage of 8 kV to the corona discharger arranged at a distance of 1 mm from the surface to generate a corona discharge to charge the surface, the maximum value of the surface potential after 0.3 second is 300 V. The image display device in any one of said 1-3 which is larger particle | grains.

5. The image display device according to any one of the above 1 to 4, wherein the anisotropic conductive film is formed by dispersing conductive particles in a thermosetting adhesive or a photocurable adhesive.

6. Said image display apparatus of said 5 whose diameter of electroconductive particle disperse | distributed in thermosetting adhesive or photocurable adhesive is 0.1-20 micrometers.

7. The image display device according to 5 or 6 above, wherein the thermosetting adhesive or the photocurable adhesive contains at least one compound having any one of glycidyl group, acryl group and methacryl group.

A second embodiment of the first invention of the present invention relates to a new type of dry image display device which has been studied in view of the above circumstances, and is inexpensive and stable in an apparatus for repeatedly displaying an image using static electricity. At the same time, it is an object to mount an electrode or the like in a short time, and to efficiently manufacture an image display device having excellent performance.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, the present inventors showed high response speed by using the sorting body which combines the fluidity | liquidity which is a characteristic of a liquid, and the constant shape retention which is a characteristic of a solid, and it is inexpensive and improves stability. An entirely new image display device which achieves both reduction of the driving voltage and the reduction of the driving voltage is obtained, and by attaching a member such as an electrode which sends a signal applied to a circuit to display an image to the substrate with an anisotropic conductive film, It has been found that the image display device can be manufactured efficiently, and the present invention has been reached.

That is, the 2nd Embodiment of 1st invention of this invention provides the following image display apparatuses.

1. An image display apparatus for enclosing a sorting body exhibiting high fluidity in an aerosol state in which a solid substance stably floats as a dispersoid in a gas between at least two opposing substrates, wherein the sorting body is moved. An image display apparatus, wherein a member for sending a signal applied to a circuit of a display is mounted on a substrate by an anisotropic conductive film.             

2. The image display device of 1 above, wherein the appearance volume at the time of maximum floating of the fractional body is at least twice as large as that at the time of non-floating.

3. The image display device according to 1 or 2 above, wherein the change in time of the appearance volume of the classification body satisfies the following equation.

V ₁₀ / V ₅ > 0.8

Here, V ₅ represents the apparent volume (cm 3) of the fraction after 5 minutes from the maximum floating time, and V ₁₀ represents the apparent volume (cm 3) of the fraction after 10 minutes from the maximum floating time.

4. The image display device according to any one of the above 1 to 3, wherein the average particle diameter (d (0.5)) of the particulate matter constituting the classification body is 0.1 to 20 µm.

5. The image display device according to any one of the above 1 to 4, wherein the anisotropic conductive film is formed by dispersing conductive particles in a thermosetting adhesive or a photocurable adhesive.

6. Said image display apparatus of said 5 whose diameter of electroconductive particle disperse | distributed in thermosetting adhesive or photocurable adhesive is 0.1-20 micrometers.

7. The image display device according to 5 or 6 above, wherein the thermosetting adhesive or the photocurable adhesive contains at least one compound having any one of glycidyl group, acryl group and methacryl group.

A first embodiment of the second invention of the present invention is to provide an image display apparatus using a dry electrostatic display panel, which is simple in structure and excellent in stability and integrated with an optical function member for obtaining a clear image. The purpose is to.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, as a result, at least one particle group is enclosed between two board | substrates which at least one is transparent, and the particle group is made to the particle group with two types of electrodes from which an electric potential differs. By integrating the image display panel for moving the particles to display an image by applying an electrostatic field and the optical function member with a transparent elastic layer interposed therebetween, a simple structure, excellent stability and a clear image can be obtained. The present invention has been reached.

That is, the 1st Embodiment of 2nd invention of this invention provides the following image display apparatuses.

1. an image display panel for enclosing at least one kind of particle group between two substrates at least one of which are transparent, and applying an electrostatic field to the particle group at two kinds of electrodes having different potentials to move the particles to display an image; And an optical function member, wherein the image display panel and the optical function member are integrated with a transparent elastic layer interposed therebetween.

2. The said 1 image display apparatus whose average particle diameter of a particle | grain is 0.1-50 micrometers.

3. The image display device of 1 or 2 above, wherein the surface charge density of the particles is 5 to 150 µC / m 2 in absolute value.

4. When the particles apply a voltage of 8 kV to the corona discharger arranged at a distance of 1 mm from the surface to generate a corona discharge to charge the surface, the maximum value of the surface potential after 0.3 second is 300 V. The image display device in any one of said 1-3 which is larger particle | grains.

5. When the refractive index of the transparent elastic layer is n ₀ , the refractive index of the optical function member is n ₁ , and the refractive index of the transparent substrate of the image display panel is n ₂ , the absolute value of the difference between n ₀ and n ₁ , and The image display device according to any one of the above 1 to 4, wherein the absolute value of the difference between n ₀ and n ₂ is respectively 0.2 or less.

6. In the case where the transparent elastic layer has a strain (ε ₀ ) at 25 ° C., which is a stress relaxation property, as 5%, and an initial value (after 0.05 seconds) of the stress relaxation modulus as G ₀ , G ₀ is 6.5 × 10. ⁶ Pa or less, the relationship between the stress relaxation modulus (G) and the time (t (seconds)) obtained from the damping curve of the stress relaxation modulus,

lnG (t) = -t / τ + lnG ₀

The image display device according to any one of the above 1 to 5, wherein the stress relaxation time (τ) calculated by the above is 17 seconds or less.

A second embodiment of the second invention of the present invention relates to a new type of dry image display device that has been studied in view of the above circumstances, and is inexpensive and stable in a method of repeatedly displaying an image using static electricity. An object of the present invention is to provide an image display device which is excellent in integration with an optical function member and obtains a clear image.             

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, the present inventors showed the high response speed, inexpensive, and stability by using the classifier which combines the fluidity | liquidity which is a characteristic of a liquid, and the constant external shape maintenance characteristic which is a characteristic of a solid. An image display panel that achieves both an improvement and a reduction in driving voltage is obtained, and by integrating the image display panel and the optical function member with a transparent elastic layer interposed, a new image display device integrated with the optical function member from which a clear image is obtained is obtained. And the present invention was reached.

That is, the 2nd Embodiment of 2nd invention of this invention provides the following image display apparatuses.

1. An image display panel for enclosing a classification body exhibiting high fluidity in an aerosol state in which a solid substance stably floats as a dispersoid in a gas between two opposing substrates at least one of which is transparent, and an optical function. And an image display panel and an optical function member are integrated with a transparent elastic layer interposed therebetween.

2. The image display device of 1 above, wherein the appearance volume at the time of maximum floating of the fractional body is at least twice as large as that at the time of non-floating.

3. The image display device according to 1 or 2 above, wherein the change in time of the appearance volume of the classification body satisfies the following equation.

V ₁₀ / V ₅ > 0.8

Here, V ₅ represents the apparent volume (cm 3) of the fraction after 5 minutes from the maximum floating time, and V ₁₀ represents the apparent volume (cm 3) of the fraction after 10 minutes from the maximum floating time.

4. The image display device according to any one of 1 to 3, wherein the average particle diameter (d (0.5)) of the fraction is 0.1 to 20 µm.

5. When the refractive index of the transparent elastic layer is n ₀ , the refractive index of the optical function member is n ₁ , and the refractive index of the transparent substrate of the image display panel is n ₂ , the absolute value of the difference between n ₀ and n ₁ , and The image display device according to any one of the above 1 to 4, wherein the absolute value of the difference between n ₀ and n ₂ is respectively 0.2 or less.

6. In the case where the transparent elastic layer has a strain (ε ₀ ) at 25 ° C., which is a stress relaxation property, as 5%, and an initial value (after 0.05 seconds) of the stress relaxation modulus as G ₀ , G ₀ is 6.5 × 10. ⁶ Pa or less, the relationship between the stress relaxation modulus (G) and the time (t (seconds)) obtained from the damping curve of the stress relaxation modulus,

lnG (t) = -t / τ + lnG ₀

The image display device according to any one of the above 1 to 5, wherein the stress relaxation time (τ) calculated by the above is 17 seconds or less.

A first embodiment of the third invention of the present invention is a dry electrostatic image display device, which has a simple structure, is excellent in stability, improves light transmittance, achieves high contrast, and provides a clearer image. It is to be done.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective in a dry electrostatic image display apparatus, the present inventors enclosed one or more types of particle group between two board | substrates which at least one is transparent, and two types from which a potential differs. A plurality of layers having different refractive indices are formed on the surface of a transparent substrate of an image display device that imparts an electric field to the particle group at an electrode of the electrode to display an image, thereby providing a simple structure, excellent stability, and reflection of external light. Was suppressed, the light transmittance was increased, high contrast was achieved, and a clear image was obtained, and the present invention was reached.

That is, the first embodiment of the third invention of the present invention provides the following image display device.

1. An image display apparatus in which at least one particle group is enclosed between two opposing substrates, and two kinds of electrodes having different potentials are used to impart an electric field to the particle group to move the particles to display an image. And an antireflection layer comprising a plurality of layers having different refractive indices on a surface of the transparent substrate.

2. The said 1 image display apparatus whose average particle diameter of a particle | grain is 0.1-50 micrometers.

3. The image display device of 1 or 2 above, wherein the surface charge density of the particles is 5 to 150 µC / m 2 in absolute value.

4. When the particles apply a voltage of 8 kV to the corona discharger arranged at a distance of 1 mm from the surface to generate a corona discharge to charge the surface, the maximum value of the surface potential after 0.3 second is 300 V. The image display device in any one of said 1-3 which is larger particle | grains.

5. The antireflection layer is formed by stacking a low refractive layer formed by sputtering using a conductive silicon carbide as a target and a high refractive layer formed by sputtering using a conductive titanium oxide as a target. An image display device according to one item.

6. The image display device of 5 above, wherein the antireflection layer prevents reflection of light of 380 to 780 nm and the light reflectivity is 10% or less.

A second embodiment of the third invention of the present invention relates to a new type of dry image display device that has been studied in view of the above circumstances, and has a simple structure and is inexpensive in a method of repeatedly displaying an image using static electricity. Further, an object of the present invention is to provide an image display device which is excellent in stability, further increases light transmittance, achieves high contrast, and obtains a clearer image.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, the present inventors showed the high response speed, inexpensive, and using the sorting body which combines the fluidity | liquidity which is a characteristic of a liquid, and the constant appearance retention which is a characteristic of a solid, It was found that an image display device excellent in stability was obtained, and that a clear image was obtained by forming an antireflection layer on a transparent substrate to improve visibility, thereby reaching the present invention.

That is, the 2nd Embodiment of 3rd invention of this invention provides the following image display apparatuses.             

1. An image display apparatus in which a sorting body exhibiting high fluidity is enclosed between two opposing substrates at least one of which is transparent, in which a solid substance is stably suspended as a dispersoid in a gas to move the sorting body. An anti-reflection layer made of a plurality of layers having different refractive indices is formed on a surface of a substrate.

2. The image display device of 1 above, wherein the appearance volume at the time of maximum floating of the fractional body is at least twice as large as that at the time of non-floating.

3. The image display device according to 1 or 2 above, wherein the change in time of the appearance volume of the classification body satisfies the following equation.

V ₁₀ / V ₅ > 0.8

Here, V ₅ represents the apparent volume (cm 3) of the fraction after 5 minutes from the maximum floating time, and V ₁₀ represents the apparent volume (cm 3) of the fraction after 10 minutes from the maximum floating time.

4. The said 1-3 display image apparatus whose average particle diameter (d (0.5)) of the particle | grains which comprise a classification body is 0.1-20 micrometers.

5. The antireflection layer is any one of the above 1 to 4, wherein the low refractive layer formed by sputtering using conductive silicon carbide as a target and the high refractive layer formed by sputtering using conductive titanium oxide as a target are stacked on each other. An image display device according to one item.

6. The image display device according to any one of the above 1 to 5, wherein the antireflection layer prevents reflection of light of 380 to 780 nm and the light reflectivity is 10% or less.

The first embodiment of the fourth invention of the present invention is an image display apparatus which is dry, has a fast response performance, a simple structure, is inexpensive, and has excellent stability, and there is no positional displacement between substrates, and particles can be prevented from leaking. It is an object of the present invention to provide an image display device having an image display plate capable of obtaining high image display accuracy.

The image display device according to the first embodiment of the fourth aspect of the present invention encloses two or more kinds of particle groups having different colors and charging characteristics between two substrates at least one of which is transparent, and at least one of the substrates An image display device comprising an image display plate for applying an electric field to the particle group and moving the particles to display an image in an electrode pair composed of electrodes formed on both sides, wherein two substrates of the image display plate are formed by a thermosetting adhesive or It connects using a photocurable adhesive agent.

In the image display panel used in the image display apparatus according to the first embodiment of the fourth invention of the present invention, two substrates, specifically, a transparent substrate and an opposing substrate are connected by using a thermosetting adhesive or a photocuring adhesive to bond the adhesive. After setting two board | substrates to a predetermined position through this, an adhesive can be hardened in a short time by irradiating heat or light, and the position shift between board | substrates and leak of a particle can be eliminated. Thereby, the high image display precision of an image display board can be implement | achieved.

As a thermosetting adhesive or photocurable adhesive agent in the image display apparatus which concerns on the 1st Example of 4th invention of this invention, the adhesive agent containing 1 or more types of compounds which have glycidyl group, an acryl group, and methacryl group is used. It is desirable to. As particle | grains in the image display apparatus of this invention, it is preferable that the average particle diameter of a particle | grain is 0.1-50 micrometers. Moreover, it is preferable that the surface charge density of particle | grains is 5-150 micrometer / m <2> in absolute value. And when particle | grains apply the voltage of 8 kV to the corona discharger arrange | positioned at intervals of 1 mm with the surface, and generate | occur | produce a corona discharge and charge the surface, the maximum value of the surface potential after 0.3 second is 300V. It is preferred to be larger particles.

A second embodiment of the fourth invention of the present invention is an image display device that exhibits a high response speed, is inexpensive, and achieves both an improvement in stability and a reduction in driving voltage. It is an object of the present invention to provide an image display device having an image display plate that can prevent leakage of a sieve and obtain high image display accuracy.

The image display device according to the second embodiment of the fourth invention of the present invention is a classification showing high fluidity in an aerosol state in which a solid substance is stably suspended as a dispersoid in a gas between at least one of the two opposing substrates that is transparent. An image display apparatus comprising an image display panel for enclosing a sieve, applying an electric field to the classifying body from an electrode pair formed of electrodes formed on one or both of the substrates, and moving the classifying body to display an image. Two board | substrates of a display panel are connected using a thermosetting adhesive or a photocuring adhesive. It is characterized by the above-mentioned.

As the image display panel used in the image display apparatus according to the second embodiment of the fourth invention of the present invention, two substrates, specifically, a transparent substrate and an opposing substrate are connected by using a thermosetting adhesive or a photocuring adhesive, After setting two board | substrates to a predetermined position via an adhesive agent, an adhesive can be hardened | cured in a short time by irradiating heat or light, and the position shift between board | substrates and leakage of a classification body can be eliminated. Thereby, the high image display precision of an image display board can be implement | achieved.

As a thermosetting adhesive or photocurable adhesive agent in the image display apparatus which concerns on the 2nd Example of 4th invention of this invention, the adhesive agent containing one or more types of compounds which have glycidyl group, an acryl group, and a methacryl group is used. It is preferable. As the classification body in the image display device of the present invention, it is preferable that the external appearance volume at the time of maximum floating of the classification body is two times or more than the non-floating. In addition, it is preferable that the time change of the apparent volume of the fraction is V ₁₀ / V ₅ > 0.8 (V ₅ is the apparent volume (cm 3) of the fraction after 5 minutes from the maximum suspension, and V ₁₀ is ₁₀ from the maximum suspension. The external appearance volume (cm <3>) of the fraction after minutes is shown.). And it is preferable that the average particle diameter (d (0.5)) of the particle | grain material which comprises a classification body is 0.1-20 micrometers.

The first embodiment of the fifth invention of the present invention solves the above-described problems, and in the image display device having a quick response speed, a simple structure, a low cost, and excellent stability, the display area can be further increased. It is an object of the present invention to provide an image display device that can simplify the handling of particles during manufacture.

In the image display device according to the first embodiment of the fifth aspect of the present invention, at least one of two types of particle groups having different colors and charging characteristics is enclosed between two opposing substrates which are transparent, and two kinds having different potentials. An image display device comprising an image display panel for applying an electric field to a particle group at an electrode of an electrode to move particles to display an image, wherein the image display device has one or more image display elements separated from each other by a partition wall, The bottom width wb on the opposite substrate side is larger than the head width wt on the transparent electrode side.

In the first embodiment of the fifth invention of the present invention, the partition wall portion is in contact with the transparent substrate by making the shape of the partition wall larger than the width of the bottom portion (wb) of the opposing substrate side than the head portion width (wt) of the transparent electrode side. , The display area can be increased, and when the particle group is filled inside the image display element surrounded by the partition wall, the particles remaining in the head portion of the partition wall can be reduced, and the particle group at the time of manufacture Can simplify handling.

As a preferable example in the first embodiment of the fifth aspect of the present invention, the ratio (wt / wb) of the bottom width wb on the opposite substrate side to the width of the head width wt on the transparent substrate side is 0.5 or less, The average particle diameter of the particles is 0.1 to 50 µm, and the absolute value of the difference between the surface charge densities of the two kinds of particles measured by the blow-off method using the same kind of carrier is 5 µC / m 2 to 150 µC / m 2. When the particle | grains and the particle | grains apply the voltage of 8 kV to the corona discharger arrange | positioned at intervals of 1 mm from the surface, and generate | occur | produce a corona discharge and charge the surface, the maximum value of the surface potential after 0.3 second is more than 300V. There are ones that are large particles and ones that have white and black colors in two kinds of particle groups. In any case, the image display device of the present invention can be obtained more preferably.             

The second embodiment of the fifth aspect of the present invention solves the problems described above, and provides a larger display area in an image display device having a quick response speed, a simple structure, a low cost, and excellent stability. It is an object of the present invention to provide an image display device which can simplify the handling of a sorting body during manufacture.

An image display device according to a second embodiment of the fifth aspect of the present invention is a classification showing high fluidity in an aerosol state in which a solid substance stably floats as a dispersoid in a gas between at least one of two opposing substrates that is transparent. An image display device comprising an image display panel which encloses a sieve, imparts an electric field to the sorting body in an electrode pair consisting of electrodes having different potentials, and moves the sorting body to display an image, wherein the image display device is isolated from each other by a partition wall. In addition to having at least two image display elements, the shape of the partition wall is characterized in that the bottom width wb on the opposing substrate side is larger than the head width wt on the transparent substrate side.

In the second embodiment of the fifth invention of the present invention, the portion of the partition wall which contacts the transparent substrate by making the shape of the partition wall larger than the width of the bottom portion (wb) of the opposing substrate side than the head portion width (wt) of the transparent substrate side , The display area can be increased, and when the classifier is filled inside the image display element enclosed by the partition wall, the classifier remaining in the head portion of the partition wall can be reduced, thereby classifying at the time of manufacture. Handling of the sieve can be simplified.

As a preferable example in the second embodiment of the fifth invention of the present invention, the ratio (wt / wb) of the bottom width wb on the opposite substrate side to the width of the head width wt on the transparent substrate side is 0.5 or less, is to be the exterior volume of the maximum suspension of the classification element more than twice the tail Yushi, the time variation of the exterior volume of the classified material satisfies the following _{expression, V 10 / V 5> 0.8} (V 5 5 from the maximum floating The apparent volume (cm 3) of the fraction after minutes, V ₁₀ represents the apparent volume (cm 3) of the fraction after 10 minutes from the maximum suspension, and the average particle diameter (d (0.5) of the particulate matter constituting the fraction. )) Is 0.1-20 micrometers. In any case, the image display device of the present invention can be obtained more preferably.

The first embodiment of the sixth invention of the present invention solves the above-described problems, and in the method of manufacturing an image display device having a fast response speed, a simple structure, a low cost, and excellent stability in a dry manner, It is an object of the present invention to provide a method for manufacturing an image display apparatus which can maintain a high bonding strength of a substrate and does not leak particles to the outside.

The manufacturing method of the image display apparatus which concerns on the 1st Example of 6th invention of this invention encloses two or more types of particle groups from which a color and a charging characteristic differ, between two board | substrates which oppose at least one, A manufacturing method of an image display apparatus comprising an image display plate having one or more image display elements separated from each other by partition walls by applying an electric field to a particle group at two different kinds of electrodes to move the particles to display an image. A partition wall is formed in one or both of the said transparent board | substrate and an opposing board | substrate, an adhesive agent is formed in the front-end | tip of a partition, and the partition and the other board | substrate or partitions were joined together through the adhesive agent, It is characterized by the above-mentioned.             

In the first embodiment of the sixth invention of the present invention, a partition wall is formed on one or both of the transparent substrate and the opposing substrate, and an adhesive is formed at the tip of the partition wall to join the partition wall and the other substrate or partition walls through the adhesive. By doing so, the bonding between the partition and the substrate or the bonding between the partitions can be strengthened, and the particles can be almost completely sealed.

As a preferable example in the second embodiment of the sixth invention of the present invention, the average particle diameter of the particles is 0.1-50 占 퐉, and the two kinds of particles measured by the blow-off method using the same kind of carrier, The absolute value of the difference between the surface charge densities is 5 to 150 µC / m 2, and the particles are subjected to a corona discharge by applying a voltage of 8 kV to a corona discharger arranged at a distance of 1 mm from the surface to generate a corona discharge. In the case, the maximum value of the surface potential after 0.3 second is a particle larger than 300 V, and the color of the two kinds of particle groups may be white and black. In any case, the manufacturing method of the image display apparatus of this invention can be implemented more preferably.

Moreover, the image display apparatus which concerns on the 1st Example of 6th invention of this invention is characterized by manufacturing according to the manufacturing method of the image display apparatus mentioned above.

The second embodiment of the sixth invention of the present invention solves the above-described problems, and in the method of manufacturing an image display device having a fast response speed, a simple structure, a low cost, and excellent stability in a dry manner, It is an object of the present invention to provide a method for manufacturing an image display device which can maintain a high bonding strength of a substrate and which does not leak out the classifier, and an image display device manufactured by the method.             

The manufacturing method of the image display apparatus which concerns on the 2nd Example of 6th invention of this invention is a high fluidity | liquidity in the aerosol state in which solid substance stably floats as a dispersoid in a gas between two board | substrates of which at least one is transparent. At least one image display element isolated from each other by a partition wall by enclosing a sorting body indicative of an electrode and applying an electric field to the sorting body in an electrode pair composed of electrodes having different potentials, thereby moving the sorting body to display an image. A manufacturing method of an image display device having an image display panel having a barrier rib, wherein a barrier rib is formed on one or both of the transparent substrate and the opposing substrate, and an adhesive is formed at the tip of the barrier rib to bond the adhesive to the barrier rib and the other substrate or barrier ribs. It is characterized in that bonded through.

In the second embodiment of the sixth invention of the present invention, a partition wall is formed on one or both of the transparent substrate and the counter substrate, and an adhesive is formed at the tip of the partition wall to join the partition wall and the other substrate or partition walls through the adhesive. By doing so, the bonding between the partition wall and the substrate or the bonding between the partition walls can be strengthened, and the fraction can be almost completely sealed.

As a preferable example in the second embodiment of the sixth invention of the present invention, the apparent volume at the time of maximum suspension of the fraction is not less than twice that of non-floating, and the time change in the apparent volume of the fraction is such that the following equation is satisfied. , V ₁₀ / V ₅ > 0.8 (V ₅ represents the apparent volume (cm 3) of the fraction after 5 minutes from the maximum suspension, and V ₁₀ represents the apparent volume (cm 3) of the fraction after 10 minutes from the maximum suspension.) And the average particle diameter (d (0.5)) of the particulate matter constituting the fractional body may be 0.1 to 20 µm. In any case, the manufacturing method of the image display apparatus of this invention can be implemented more preferably.

Moreover, the image display apparatus which concerns on the 2nd Example of 6th invention of this invention is characterized by manufacturing according to the manufacturing method of the image display apparatus mentioned above.

In addition, the "classification body" in this invention is a substance of both intermediate states which combines the characteristic of a fluid and particle | grains which shows fluidity by itself, without borrowing the force of a gas or a liquid. For example, a liquid crystal is defined as an intermediate phase between a liquid and a solid, and has liquidity and liquid anisotropy (optical properties) characteristic of a solid (Heibonsha: Encyclopedia). On the other hand, the definition of particles is an object with a finite mass, even if it is negligible in size, and is subject to gravity (Maruzen: Physics Dictionary). Here, even in the particles, there are special states such as a contributing fluidized bed and a liquid-liquid fluid, and when the gas flows from the bottom plate to the particles, the upward force is applied to the particles in response to the velocity of the gas, and when the force is in harmony with gravity It is said that a fluid that is easily moved like a fluid is called a fluidized bed, and a state that is fluidized by a fluid is also called a liquid fluid (Heibonsha: Encyclopedia). As described above, the high-density fluidized bed and the liquid-liquid fluid are in a state of using gas or liquid flow. In the present invention, it has been found that the substance can be specifically produced without showing the force of the gas and the force of the liquid, and this is defined as a classification body.

In other words, the classifier in the present invention is an intermediate state having both characteristics of particles and liquids, similar to the definition of liquid crystal (middle phase of liquid and solid), and is very hard to be affected by gravity, which is a characteristic of the aforementioned particles. It is a substance that exhibits a unique state that shows the same sex. Such a substance can be obtained in an aerosol state, that is, in a dispersion system in which a solid or liquid substance stably floats as a dispersoid in a gas, and the solid substance is a dispersoid in the image display device of the present invention.

Brief description of the drawings

BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing which shows an example of the image display board display system in the image display apparatus of this invention.

It is explanatory drawing which shows the other example of the image display board display system in the image display apparatus of this invention.

3 is an explanatory diagram showing a structure of an example of an image display plate in the image display device of the present invention.

4 is an explanatory diagram showing still another example of the display system in the image display device of the present invention.

5 is an explanatory diagram showing another example of a display method in the image display device of the present invention.

6 is an explanatory diagram showing a structure of another example in the image display device of the present invention.

7 (a) to 7 (c) are diagrams showing still another example of the structure of the image display element of the image display panel constituting the image display device of the present invention, and the display driving principle thereof.

8 is a diagram illustrating a configuration of still another example of an image display element of an image display panel constituting the image display device of the present invention.

9 is a diagram illustrating an example of a partition wall shape in the image display device of the present invention.

It is a figure which shows the measuring method of the surface potential of the particle | grains used for the image display apparatus of this invention.

It is explanatory drawing which shows the relationship between the applied voltage and reflection density in evaluation of the display function of the image display apparatus of this invention.

12 is a diagram showing the optical performance of the antireflection layer produced in the example.

13 (a) to 13 (c) are diagrams each showing a board-to-board connection process in the image display device of the present invention.

14A to 14C are explanatory diagrams each showing an example of a display element in the image display device of the present invention and its display operation principle.

15 (a) and 15 (b) are longitudinal cross-sectional views each showing an example of a partition shape used in the image display device of the present invention.

It is explanatory drawing which shows the case where a display electrode is arrange | positioned on a transparent substrate and the counter electrode is arrange | positioned at an opposing board | substrate as another example of the display element in the image display apparatus of this invention.

17 is a view for explaining a method of forming a partition in the image display device of the present invention.

18 is a diagram for explaining another method of forming the partition wall in the image display device of the present invention.

19 is a view for explaining a method of forming a partition in the image display device of the comparative example.

It is a figure which shows an example of the manufacturing method of the partition which forms the image display element in the manufacturing method of the image display apparatus of this invention.

It is a figure which shows the other example of the manufacturing method of the partition which forms the image display element in the manufacturing method of the image display apparatus of this invention.

22 is a view for explaining a method of forming a partition in the image display device of the present invention.

Fig. 23 is a view for explaining another method of forming the partition wall in the image display device of the present invention.

24 is a view for explaining a method of forming a partition in the image display device of the comparative example.

Best Mode for Carrying Out the Invention

First, the various structures of the image display apparatus used as object of this invention are demonstrated in order. In the following description, in each of the first to sixth inventions, the first embodiment and the second embodiment exist, the first embodiment each shows an example of particles, and the second embodiment shows an example of a classifier. It is shown.             

In the first embodiment using the particles of the image display plate used in the image display device of the present invention, one or more kinds of particles 6 are enclosed between the transparent substrate 1 and the opposing substrate 2, and two kinds having different potentials. The electric field is transmitted from the electrodes 3 and 4 to the particles 5 and 6, and the particles 5 and 6 are moved to display an image.

The force applied to the particles 5 and 6 can be considered to be a force attracted by the Coulomb force between the particles, an electric imaging force with the electrode plate, an intermolecular force, a liquid crosslinking force, gravity, and the like.

As shown in FIG. 1, this image display is a display system by moving two or more kinds of different particles in a vertical direction with a substrate, and as shown in FIG. 2, a particle of one color in a direction parallel to the substrate. Although there is a display system by moving, it can be applied to any, but it is preferable to apply to the former system in view of stability.

3 is an explanatory diagram showing the structure of the image display device according to the first embodiment in each example of the present invention, and is formed by opposing substrates 1, 2, and particles 5, 6, The partition 7 is formed as needed.

Also in the second embodiment using the classifier of the image display in the image display apparatus of the present invention, as shown in FIG. 4, the classifiers 5 and 6 having different colors from two or more kinds are different as shown in FIG. 4. The display method of moving the substrate 1 and 2 in the vertical direction and the display system of moving the sorting member 6 of one color in parallel with the substrate 1 and 2 as shown in FIG. Although the former method is preferable in terms of stability.             

6 is an explanatory diagram showing a structural example of an image display device according to a second embodiment in each example of the present invention. That is, the image display apparatus of this invention is formed by the opposing board | substrate 1, the board | substrate 2, the sorting bodies 5 and 6 which exist between these board | substrates, and the partition 7 formed as needed.

7 (a) to 7 (c) are diagrams showing still another example of the structure of the image display element of the image display panel constituting the image display device of the present invention and the display driving principle thereof. In the example shown to Fig.7 (a)-(c), the code | symbol 1 is a transparent substrate, 2 is a counter substrate, 3 is a display electrode, 4 is a counter electrode, 5 is negatively charged particle, 6 is positively charged particle, 7 is a partition and 8 is an insulator.

In the example shown to FIG. 7A, the negatively charged particle 5 and the positively charged particle 6 are arrange | positioned between the opposing board | substrates (transparent board | substrate 1 and the opposing board | substrate 2). When a voltage is applied such that the display electrode 3 side has a low potential and the counter electrode 4 side has a high potential in this state, as shown in FIG. 7B, the positively charged particles 6 are caused by a coulomb force. Moves to the display electrode 3 side, and the negatively charged particles 5 move to the opposite electrode 4 side. In this case, the display surface seen from the transparent substrate 1 side is seen by the color of the positively charged particles 6. Next, when the potential is switched and a voltage is applied such that the display electrode 3 side has a high potential and the counter electrode 4 side has a low potential, as shown in FIG. 7C, negatively charged particles are caused by a coulomb force. 5 moves to the display electrode 3 side, and the positively charged particles 6 move to the opposite electrode 4 side. In this case, the display surface seen from the transparent substrate 1 side is seen by the color of the negatively charged particles 5.             

7 (b) and 7 (c) can be repeatedly displayed by simply inverting the potential of the power source, and the color can be reversibly changed by inverting the potential of the power source. The color of the particles can be selected without limitation. For example, when the negatively charged particles 5 are white and the positively charged particles 6 are black, or the negatively charged particles 5 are black and the positively charged particles 6 are white, The display is a reversible display between white and black. In this system, each particle is in a state of being adhered to the electrode by ordinary force, so that the display image is retained for a long time even after the power is turned off, and memory retention is good.

In the present invention, since each of the charged particles fly in the gas, the response speed of the image display is high, and the response speed can be 1 m / sec or less. In addition, like the liquid crystal display element, an alignment film, a polarizing plate, or the like is unnecessary, the structure is simple, and a low cost and a large area are possible. It is stable against temperature changes and can be used from low to high temperatures. In addition, there is no viewing angle, high reflectivity, reflection type, easy to see even in bright places, and low power consumption. It also has memory characteristics and does not consume power when holding an image.

8 is a diagram illustrating a configuration of still another example of an image display element of an image display panel constituting the image display device of the present invention. In the example shown in FIG. 8, unlike the example shown in FIGS. 7A to 7C, the display electrode 3 is formed on the transparent substrate 1, and the counter electrode 4 is formed on the counter substrate 2. Doing. In the example shown in FIG. 8, the transparent electrode is required as the display electrode 3. In contrast, in the examples shown in FIGS. 7A and 7B, since the opaque electrode can be used as the display electrode 3, an inexpensive and low-resistance metal electrode such as copper or aluminum can be used. .

Moreover, although the example using particle | grains was demonstrated in the example shown to FIG.7 (a)-(c) and FIG.8 mentioned above, you may use a classifier.

Hereinafter, the board | substrate, an electrode, and a partition among each member used for the image display apparatus of this invention are demonstrated.

As for the substrate, at least one substrate is a transparent substrate 1 capable of confirming the color of the particles from outside the apparatus, and a material having high visible light transmittance and good heat resistance is suitable. The opposing substrate 2 may be transparent or opaque. The flexibility of the substrate is appropriately selected depending on the application, and for example, a material that is flexible for applications such as electronic paper, and a material that is not flexible for applications such as display of mobile devices in mobile phones, PDAs, and notebook computers Suitable. Examples of the substrate material include polymer sheets such as polyethylene terephthalate, polyether sulfone, polyethylene, polycarbonate, polyimide and acrylic, and inorganic sheets such as glass and quartz. The thickness of the substrate is preferably 2 µm to 5000 µm, particularly preferably 5 to 1000 µm. If the thickness is too thin, it is difficult to maintain the strength and the uniformity of the spacing between the substrates. If the thickness is too thick, the sharpness and contrast reduction of the display function occur. In particular, in the case of electronic paper use, flexibility is inferior.

In the image display apparatus of the present invention, there are cases where an electrode is not formed on a substrate and an electrode is formed.

In the case of not forming an electrode, a latent electrostatic image is applied to the outer surface of the substrate, and a group of particles or fractions containing color charged with predetermined characteristics by an electric field generated by the electrostatic latent image is pulled to the substrate, or By repulsion, the particle group or sorting body arrange | positioned corresponding to the latent electrostatic image is visually recognized outside the display apparatus through a transparent substrate. The electrostatic latent image may be formed by transferring an electrostatic latent image formed by a conventional electrophotographic system onto a substrate using an electrophotographic photosensitive member, or directly forming an electrostatic latent image by ion flow.

The display method in the case of forming an electrode is performed by pulling or repulsing a particle group or fraction of a color charged with predetermined characteristics by an electric field generated at each electrode position on a substrate by an external voltage input to an electrode portion. The particle group or the sorting body arranged corresponding to the potential is visually recognized from the outside of the display device through the transparent substrate.

The electrode at this time is formed of a transparent and patternable conductive material, the electrode thickness of which can secure the conductivity and is free of light transmittance, and is preferably 3 to 1000 nm, preferably 5 to 400 nm. . In this case, the external voltage input may overlap DC or AC.

In the image display apparatus of this invention, it is preferable to form the partition 7 as shown in each figure around four of each display element. A partition can also be formed in two parallel directions. As a result, extra particle movement in the parallel direction of the substrate can be prevented, thereby improving durability and memory retention, and also increasing the strength of the image display panel by uniformly reinforcing the space between the substrates. That is, in the image display apparatus of the present invention, it is preferable to form partition walls connecting the opposing substrates in order to prevent extra movement in the substrate parallel direction of particles or sorting bodies, and to configure the display portion by a plurality of display cells.

The shape of the partition wall 7 is appropriately optimally set by the particles or fractions related to the display and is not limited in general, but the width of the partition wall is adjusted to 1 to 100 µm, preferably 2 to 50 µm, The height is 10 to 5000 µm, preferably 10 to 500 µm.

Moreover, when forming a partition, both the rib method of joining after forming a rib in each of the opposing board | substrates, and the rib method of forming a rib only on one board | substrate can be considered, but in the image display apparatus of this invention, it joins Formation of the partition wall by the single rib method is preferable in order to prevent the shift | offset | difference of city.

As for the display cell formed by the partition wall which consists of these ribs, as shown in FIG. 9, a rectangle, a triangle, a line form, a circle, and a hexagon (honeycomb structure) are illustrated from a board | substrate plane direction.

It is preferable that the portion (area of the display cell edge portion) corresponding to the partition wall section portion seen from the display side be made as small as possible, and the sharpness of the image display is increased.

Although it does not specifically limit as a formation method of the partition 7, For example, the screen printing method which overlaps apply | coats a paste to a predetermined position using a screen board, or apply | coats all the partition materials of desired thickness on a board | substrate, and leaves it as a partition. Only the desired portion is coated with the resist pattern on the partition wall material, and then the blast material is sprayed to remove and remove the partition material other than the partition wall, or a resist pattern is formed on the substrate using a photosensitive resin. The resist is removed by filling the paste into the recessed portion of the resist and then applying the photosensitive resin composition containing the partition material onto the substrate to obtain a desired pattern by exposure and development. After apply | coating the photosensitive paste method or the paste containing a partition material on the board | substrate, the metal mold | die etc. which have an unevenness | corrugation are pressed and pressed. Type is employed by a number of methods such as mold forming method of forming the partition wall. Moreover, the relief molding method which employs the molding method and uses the relief pattern formed with the photosensitive resin composition as a mold is also employ | adopted.

Next, the particles used in the first embodiment of each invention will be described.

The particles used for display in the first embodiment of the image display apparatus of the present invention are negative or positively charged colored particles, which may be any of those moving by a Coulomb force, but are particularly spherical and small specific gravity particles. Is suitable. The particles will be single index and particles of white or black color are preferably used. The average particle diameter of the particles is preferably 0.1 to 50 µm, particularly preferably 1 to 30 µm. If the particle diameter is smaller than this range, the charge density of the particles is too large, the ordinary force on the electrode or the substrate is too strong and the memory is good, but the tracking ability when the electric field is inverted is poor. On the contrary, when the particle diameter is larger than this range, the followability is good but the memory is bad.

The method of charging the particles negatively or positively is not particularly limited, but a method of charging particles such as a corona discharge method, an electrode injection method, or a friction method is used. The charge amount of the particles naturally depends on the measurement conditions, but the charge amount of the particles in the image display device is almost dependent on the initial charge amount, the contact with the substrate, the contact with the particles of different types, and the charge attenuation according to the elapsed time. In particular, it is known that the saturation value of charging behavior due to "contact with particles of different types", that is, contact between two particles, is the governing factor. Therefore, it is important to know the difference in charging characteristics between the two particles, that is, the difference in work function, in the amount of charging, but this is difficult for simple measurement.

As a result of earnest examination, the present inventors found that the blowoff method can be relatively evaluated by measuring the charge amount of each particle by using the same carrier, and defining this by the surface charge density, thereby determining the appropriate amount of particles suitable as an image display device. We found out that we could predict charge quantity.

A detailed measuring method will be described later, and the charge amount per unit weight of the particles can be measured by sufficiently contacting the particles and the carrier particles by the blow off method and measuring the saturated charge amount thereof. The surface charge density of the particles can be calculated by separately determining the particle diameter and specific gravity of the particles.

In the image display apparatus, the particle diameter of the particles to be used is small and the influence of gravity is so small that the influence of gravity is almost negligible, so that the specific gravity of the particles does not affect the movement of the particles. However, in the charge amount of the particles, even if the average charge amount per unit weight is the same for the particles having the same particle diameter, the charge amount maintained when the specific gravity of the particles differs twice is different. Therefore, it turns out that it is preferable to evaluate the charging characteristic of the particle | grains used for an image display apparatus by the surface charge density (unit: microC / m <2>) irrespective of specific gravity of a particle | grain.             

And when there is enough difference of this surface charge density between particle | grains, two types of particle | grains hold | maintain the charge quantity of a different characteristic by contact with each other, and maintain the function which moves by an electric field.

Here, the surface charge density requires some difference in order to make the charging characteristics of the two particles different, but the larger the better, the better. In the image display device by particle movement, when the particle diameter of the particle is large, the electric imaging force tends to be a factor for determining the emergency electric field (voltage) of the particle. Therefore, in order to move the particle to a low electric field (voltage), It is good that the charge amount is low. In addition, when the particle diameter of the particles is small, non-electrical forces such as intermolecular force and liquid crosslinking force often become an emergency electric field (voltage) determinant, so that the particles move at a low electric field (voltage). In order to achieve high charge, it is preferable. However, since this depends largely on the surface properties (materials and shapes) of the particles, it cannot be uniformly defined by the particle diameter and the charge amount.

The inventors have found that the absolute value of the difference between the surface charge densities of the two kinds of particles measured by the blow-off method using the same kind of carrier in the particles having an average particle diameter of 0.1-50 µm is 5 µC / m 2 to 150 µC / m 2. It has been found that the particles can be used as an image display device in the case of.

The blow off measurement principle and method are as follows. In the blow-off method, a mixture of powder and carrier is placed in a cylindrical container netted at both ends, a high pressure gas is blown at one end to separate the powder and carrier, and only the powder is blown off (blown) from the net eye. At this time, the amount of charge opposite to the amount of charge that the powder leaves the container remains in the carrier. And all the electric charge by this electric charge collects in a Faraday cage, and the capacitor is charged by that quantity. Thus, by measuring the potential across the capacitor, the charge amount Q of the powder is obtained as Q = CV (C: capacitor capacity, V: voltage across the capacitor).

In the present invention, the charge density per unit surface area (unit: μC / m 2) is used by using TB-200 manufactured by Toshiba Chemical Co., Ltd. as a blow-off powder charge measuring device and F963-2535 manufactured by Powder Tech Co., Ltd. as the same kind of carrier. Measured.

Since the particles need to maintain their charged charge, insulating particles having a volume resistivity of 1 × 10 ¹⁰ Ω · cm or more are preferable, and insulating particles of 1 × 10 ¹² Ω · cm or more are particularly preferable.

Furthermore, the particle | grains in the image display apparatus of this invention are more preferable the particle | grains with slow charge attenuation evaluated by the method mentioned below. That is, the particles are separately formed into a film having a thickness in the range of 5 to 100 μm by pressing, heating, casting, or the like, and a corona discharge is generated by applying a voltage of 8 kV to a corona discharger disposed at a distance of 1 mm from the film surface. The surface is charged, and the change in the surface potential thereof is measured and determined. In this case, it is preferable to select and produce a particle constituent material so that the maximum value of the surface potential after 0.3 second is larger than 300V, preferably larger than 400V.

In addition, the said surface potential can be measured, for example by the apparatus (CRT2000 by QEA Corporation) shown in FIG. In the case of this apparatus, the measuring unit which keeps both ends of the roll shaft which arrange | positioned the film mentioned above on the surface by the chuck 21, and arrange | positions the small scorotron discharger 22 and the surface electrometer 23 at predetermined intervals, and is parallel. Is placed opposite to the surface of the film at a distance of 1 mm, and the measurement unit is moved at a constant speed from one end of the roll shaft to the other end with the roll shaft stopped, thereby measuring the surface potential while giving a surface charge. Method is preferably employed. The measurement environment is 25 ± 3 ° C and 55 ± 5% RH.

The particles in the image display device of the present invention may be made of any material as long as properties such as charging performance are satisfied. For example, it can form with resin, a charge control agent, a coloring agent, an inorganic additive, etc., or a coloring agent alone. Examples of the resin include urethane resins, urea resins, acrylic resins, polyester resins, acrylic urethane resins, acrylic urethane silicone resins, acrylic urethane fluorine resins, acrylic fluorine resins, silicone resins, acrylic silicone resins, epoxy resins, polystyrene resins, styrene Acrylic resins, polyolefin resins, butyral resins, vinylidene chloride resins, melamine resins, phenol resins, fluorine resins, polycarbonate resins, polysulfone resins, polyether resins, polyamide resins, and the like. Acrylic urethane resin, acrylic silicone resin, acrylic fluorine resin, acrylic urethane silicone resin, acrylic urethane fluorine resin, fluorine resin, and silicone resin are suitable in terms of controlling them. You may mix 2 or more types.

Although there is no restriction | limiting in particular as a charge control agent, As a negative charge control agent, For example, a salicylic acid metal complex, a metal-containing azo dye, a metal-containing dye (including metal ion or metal atom), quaternary ammonium salt type | system | group A compound, a calix arene compound, a boron containing compound (boron benzyl complex), a nitroimidazole derivative, etc. are mentioned. Examples of the positive charge control agent include nigrosine dyes, triphenylmethane compounds, quaternary ammonium salt compounds, polyamine resins, imidazole derivatives, and the like. In addition, metal oxides such as ultrafine silica, ultrafine titanium oxide, ultrafine alumina, nitrogen-containing cyclic compounds such as pyridine, derivatives and salts thereof, resins containing various organic pigments, fluorine, chlorine, nitrogen, and the like can also be used as charge control agents. have.

As a coloring agent, pigments and dyes of various colors, such as organic or inorganic, exemplified below, can be used.

Black pigments include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, and the like.

As a yellow pigment, chrome yellow, zinc sulfur, cadmium yellow, yellow iron oxide, mineral first yellow, nickel titanium yellow, navel yellow, naphthol yellow S, Hanzai yellow G, Hanzai yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow Lake, Permanent Yellow NCG, Tatra Gene Lake, etc.

Examples of the orange pigment include red sulfur oxide, molybdenum orange, permanent orange GTR, pyrazolone orange, balkan orange, indahslenbrilliant orange RK, benzidine oranges G, and indasrenbrilliant oranges GK.

As red pigment, Bengala, cadmium red, lead tetraoxide, mercury sulfide, cadmium, permanent red 4R, resolred, pyrazolone red, watching red, calcium salt, lake red D, brilliant carmine 6B, eosin lake, rhodamine Lake B, Alizarin Lake, Brilliant Carmine 3B.

Purple pigments include manganese, first violet B, methyl violet lake and the like.

Examples of the blue pigments include cyanide, cobalt blue, alkali blue lake, victoria blue, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chlorine, first sky blue, and inda srene blue BC.

Examples of the green pigment include chromium green, chromium oxide, pigment green B, malachite green lake, and final yellow green G.

Moreover, as a white pigment, zinc oxide, titanium oxide, antimony bag, zinc sulfide, etc. are mentioned.

Examples of the extender pigment include barite powder, barium carbonate, clay, silica, white carbon, talc, alumina white and the like.

Further, various dyes such as basic, acidic, dispersed and direct dyes include nigrosine, methylene blue, rose bengal, quinoline yellow, ultramarine blue and the like.

These coloring agents can be used individually or in combination of two or more.

Carbon black is particularly preferable as the black colorant, and titanium oxide is preferred as the white colorant.

Although it does not specifically limit about the manufacturing example of particle | grains, For example, the grinding | pulverization method and polymerization method which followed when manufacturing an electrophotographic toner can be used. Moreover, the method of coating resin, a charge control agent, etc. on the surface of an inorganic or organic pigment powder is also used.

The distance between the transparent substrate 1 and the counter substrate 2 in the image display device of the present invention may be adjusted to 10 to 5000 µm, preferably 30 to 500 µm, although particles can move and maintain contrast. do.

The particle filling amount (volume occupancy rate) is preferably filled so that the volume occupies 10 to 80%, preferably 10 to 70%, relative to the space volume between the substrates.

In the image display device of the present invention, a plurality of the display elements are used to arrange and display in a matrix. In the case of monochrome, one display element becomes one pixel. When displaying arbitrary colors other than black and white, what is necessary is just to combine the color of particle | grains suitably. In the case of full color, three types of display elements, that is, a display element having color plates of R (red), G (green) and B (blue), and each having black particles are used as one set, and a plurality of sets thereof are arranged. It is preferable to set it as an image display panel.

Next, the classification body used in the 2nd Example of each invention is demonstrated.

As described above, the classifier is a substance in the intermediate state of both the fluid and the particle, which exhibits fluidity by itself without invoking the force of the gas or the liquid. This classifier can be particularly in an aerosol state, and in the image display device of the present invention, a solid substance is used in a state in which a solid substance is relatively stably suspended as a dispersoid.

The range of the aerosol state is preferably 2 times or more, more preferably 2.5 times or more, and particularly preferably 3 times or more when the appearance volume when the fraction is maximally suspended. Although an upper limit is not specifically limited, It is preferable that it is 12 times or less.             

If the appearance volume when the fractionation body is the most suspended is less than twice the volume when it is not floating, it becomes difficult to control on the display. When the fractionation body is larger than 12 times, it is inconvenient to handle, such as flying while enclosing the classification body in the device. In addition, the external appearance volume at the time of maximum suspension is measured as follows. That is, the fractionation body is placed in a sealed container in which the fractionation body penetrates, and the container itself is vibrated or dropped to make the maximum floating state, and the appearance volume at that time is measured outside the container. Specifically, a volume of 1/5 as a sorting body when not floating in a container with a lid made of polypropylene having a diameter (inner diameter) 6 cm and a height of 10 cm (trade name Aiboy: manufactured by Azwan Corporation). The corresponding fractionation body is put, a container is set in a shaker, and the distance of 6 cm is shaken for 3 hours at 3 round trip / sec. The appearance volume immediately after shaking stop is made into the appearance volume at the time of maximum floating.

Moreover, in the image display apparatus of this invention, it is preferable that the time change of the external appearance volume of a classification body satisfy | fills following Formula.

V ₁₀ / V ₅ > 0.8

Here, V ₅ represents the appearance volume (cm 3) 5 minutes after the maximum floating time, and V ₁₀ represents the appearance volume (cm 3) 10 minutes after the maximum floating time. In addition, the image display device of the present invention preferably has appearance change with time of the volume (V ₁₀ / V ₅₎ of the classified material is greater than 0.85 and is greater than 0.9 is particularly preferred. If V ₁₀ / V ₅ 0.8 or less is becomes equal to the case of using a conventional so-called particles, it is not a high speed response as in the present invention, to secure the effect of durability.

In addition, the average particle diameter d (0.5) of the particulate matter constituting the fraction is preferably 0.1-20 탆, more preferably 0.5-15 탆, particularly preferably 0.9-8 탆. If it is smaller than 0.1 mu m, the control on the display becomes difficult. If it is larger than 20 mu m, the display can be performed, but the concealment rate decreases, making the device thinner. In addition, the average particle diameter d (0.5) of the particulate matter constituting the fractionation body is the same as d (0.5) in the next particle diameter distribution Span.

It is preferable that the particle | grain material which comprises a classification body has a particle diameter distribution (Span) shown by following formula, More preferably, it is less than three.

Particle Diameter Distribution (Span) = (d (0.9)-d (0.1)) / d (0.5)

Here, d (0.5) is a numerical value representing the particle diameter in μm that 50% of the particulate matter constituting the fraction is larger than this and 50% is smaller than this, and d (0.1) is the particle constituting the fraction smaller than this. The numerical value which shows the particle diameter of 10% of a substance by micrometer, d (0.9) is the numerical value which shows the particle diameter of 90% of the particle | grain material which comprises the fraction below this value in micrometer. By setting the particle size distribution (Span) of the particulate matter constituting the fraction to be 5 or less, the size is ordered and uniform fraction movement is possible.

The above particle diameter distribution and particle diameter can be obtained by laser diffraction / scattering method or the like. When the laser beam is irradiated to the fraction to be measured, the light intensity distribution pattern of diffraction / scattered light is spatially generated, and since the light intensity pattern corresponds to the particle diameter, the particle diameter and the particle diameter distribution can be measured. This particle diameter and particle diameter distribution are obtained from the volume reference distribution. Specifically, a Mastersizer2000 (Malvern Instruments Ltd.) measuring instrument can be used to introduce a fraction into the nitrogen stream and measure it with an accessory analysis software (soft based on volume-based distribution using Mie theory).

The preparation of the classifier may be kneaded and pulverized with a necessary resin, a charge control agent, a colorant, and other additives, may be polymerized with a monomer, and the existing particles may be coated with a resin, a charge control agent, a colorant, and other additives. Hereinafter, resin, a charge control agent, a coloring agent, and other additive which comprise a classification body are illustrated.

 Examples of the resin include urethane resins, acrylic resins, polyester resins, urethane-modified acrylic resins, silicone resins, nylon resins, epoxy resins, styrene resins, butyral resins, vinylidene chloride resins, melamine resins, phenol resins, fluorine resins, and the like. These may be mentioned, 2 or more types may be mixed, and an acrylurethane resin, an acrylurethane silicone resin, an acrylurethane fluorine resin, a urethane resin, and a fluorine resin are suitable especially from a viewpoint of controlling the adhesive force with a board | substrate.

Examples of charge control agents include quaternary ammonium salt compounds, nigrosine dyes, triphenylmethane compounds, imidazole derivatives in the case of electrostatic charge provision, and metal-containing azo dyes and salicylate metals in the case of negative charge assignment. Complexes, nitroimidazole derivatives, and the like.

Examples of the colorant include basic and acid dyes, and examples include nigrosine, methylene blue, quinoline yellow, and rose bengal.

Examples of the inorganic additives include titanium oxide, zinc oxide, zinc sulfide, antimony oxide, calcium carbonate, silver white, talc, silica, calcium silicate, alumina white, cadmium yellow, cadmium red, cadmium orange, titanium yellow, wire blue, ultramarine blue, Cobalt blue, cobalt green, cobalt violet, iron oxide, carbon black, copper powder, aluminum powder, etc. are mentioned.

However, even if such a material is kneaded without coating, it is not possible to produce a fraction showing an aerosol state. The determined formulation of the classifier indicative of the aerosol state is not exact, but is illustrated as follows.

First, it is appropriate to fix inorganic fine particles having an average particle diameter of 20-100 nm, preferably 20-80 nm, on the surface of the particulate matter constituting the fraction. And it is suitable that the inorganic fine particle is processed by the silicone oil. Examples of the inorganic fine particles include silicon dioxide (silica), zinc oxide, aluminum oxide, magnesium oxide, cerium oxide, iron oxide, copper oxide, and the like. The method of fixing these inorganic fine particles is important, for example, using a hybridizer (manufactured by Nara Machinery Co., Ltd.) or mecanofusion (manufactured by Hosokawa Micron Co., Ltd.) or the like under certain limited conditions (for example, Treatment time) can be used to produce a fraction showing the aerosol state.

In order to further improve the repeat durability, it is effective to manage the stability of the resin constituting the fraction, in particular, the water absorption rate and solvent insolubility rate. It is preferable that the water absorption of the resin constituting the classification body enclosed between the substrates is 3% by weight or less, particularly 2% by weight or less. In addition, measurement of water absorption is performed according to ASTM-D570, and measurement conditions are made into 24 hours at 23 degreeC. About the solvent insolubility of resin which comprises a classification body, it is preferable to make the solvent insolubility rate of the classification body shown by the following relational formula into 50% or more, especially 70% or more.

Solvent insoluble rate (%) = (B / A) × 100

(However, A represents the weight before the solvent immersion of the resin, B represents the weight after immersion of the resin at 25 ℃ for 24 hours in a good solvent)

If the solvent insolubility is less than 50%, bleeding occurs on the surface of the particulate matter constituting the fraction during long-term storage, affects the adhesion to the fraction and impedes the movement of the fraction, which impairs image display durability. It may be caused. Moreover, as a solvent (good solvent) at the time of measuring a solvent insolubility, methyl ethyl ketone, such as fluorine resin, methanol, etc. in polyamide resin, methyl ethyl ketone, toluene, etc. in acryl urethane resin, acetone, isopropanol, etc. in melamine resin, etc. And toluene is preferable in silicone resin.

In addition, it is preferable to adjust the filling amount of the fractionation body so that the occupancy volume of the fractionation body is 5-85%, preferably 10-65%, more preferably 15-55% of the gaps between the opposing substrates. Do. Since the classification body exhibits an aerosol state, it is difficult to encapsulate it into a display device by a conventional method, and it is suitable in terms of handling to forcibly attach the classification body to a substrate using an electrostatic coating machine. In this case, any method of adhering to only one substrate or both substrates may be used.

In addition, in the present invention, gas management of the void portion surrounding the separator between substrates is important, and contributes to improvement of display stability. Specifically, it is important to set the relative humidity at 25 ° C to 60% RH or less, preferably 50% RH or less, and more preferably 35% RH or less with respect to the gas humidity of the void portion. The above-mentioned space | gap part is occupied part of the partition body 5, 6, the occupied part of the partition 7, and the apparatus seal part in the part clamped between the transparent substrate 1 and the opposing board | substrate 2 in FIG.7 and FIG.8. The so-called fractions except for those referred to refer to the gas part in contact with each other.

The gas of the pore portion is not limited in kind as long as it is in the above-mentioned humidity range, but dry air, dry nitrogen, dry argon, dry helium, dry carbon dioxide, and dry methane are suitable. This gas needs to be enclosed in the apparatus so that the humidity is maintained. For example, the sealing material and the sealing method which perform the filling of the fractionation body, the assembly of the board, etc. under a predetermined humidity environment, and again prevent the invasion of humidity from the outside. It is important to carry out.

In addition, the image display device of the present invention is a display unit of mobile devices such as notebook computers, PDAs, mobile phones, electronic papers such as electronic books, electronic newspapers, signs such as signboards, posters, blackboards, electronic calculators, home appliances, automobiles, etc. It is used for the display part of goods, etc., and the card display part, such as a point card.

EMBODIMENT OF THE INVENTION Hereinafter, the characteristic of 1st invention-6th invention of this invention is demonstrated in order.

(About 1st invention)

The characteristic of the image display apparatus which concerns on the 1st invention of this invention is using an anisotropic conductive film for attachment of members, such as an electrode which sends the signal applied to a circuit, in order to display an image. An IC chip or the like is used as a member other than an electrode that sends a signal applied to a circuit to display an image.

Moreover, what consists of disperse | distributing electroconductive particle in a thermosetting adhesive or a photocurable adhesive agent is used for this anisotropic conductive film.             

As a thermosetting adhesive or a photocurable adhesive agent, the polymer containing one or more types of compounds which have any one of glycidyl group, an acryl group, and a methacryl group is used preferably. For example, an ethylene-vinyl acetate copolymer; a copolymer of ethylene, vinyl acetate, an acrylate-based and / or methacrylate-based monomer; a copolymer of ethylene with vinyl acetate, maleic acid and / or maleic anhydride; Copolymers of acrylate- and / or methacrylate-based monomers with maleic acid and / or maleic anhydride, and ionomer resins in which metal ions are bonded between molecules of an ethylene-methacrylic acid copolymer.

This anisotropic conductive film is obtained by adding an organic peroxide and / or a photosensitizer, a silane coupling agent, and an epoxy group-containing compound together with conductive particles to the polymer to form a film. Performance and excellent durability and heat resistance are obtained.

When the ethylene-vinyl acetate copolymer is used as the polymer, the vinyl acetate content of the ethylene-vinyl acetate copolymer is preferably 10 to 50% by weight, more preferably 15 to 45% by weight. If the vinyl acetate content is lower than 10% by weight, sufficient crosslinking degree cannot be obtained in the case of crosslinking curing at high temperature, while if it exceeds 50% by weight, the softening temperature of the resin is low and storage becomes difficult.

When using a copolymer of ethylene, vinyl acetate, and an acrylate-based and / or methacrylate-based monomer as the polymer, the vinyl acetate content of the copolymer is preferably 10 to 50% by weight, more preferably. 14-45 weight%. If the vinyl acetate content is lower than 10% by weight, sufficient crosslinking degree is not obtained in the case of crosslinking curing at high temperature. On the other hand, if the content exceeds 50% by weight, the softening temperature of the resin is low and storage is difficult, which is a practical problem. Moreover, it is preferable that the content rate of the acrylate type and / or methacrylate type monomer of the said copolymer is 0.01 to 10 weight%, More preferably, it is 0.05 to 5 weight%. When the content rate of the acrylate-based and / or methacrylate-based monomer is lower than 0.01% by weight, the effect of improving the adhesive force is lowered, while when it exceeds 10% by weight, the workability may be lowered.

As an acrylate-type and / or methacrylate-type monomer which can be used, it is a monomer chosen from an acrylic acid ester or a methacrylic acid ester monomer, and acrylic acid or methacrylic acid and C1-C20, especially 1-18 unsubstituted or epoxy group Esters with substituted aliphatic alcohols having substituents such as these are preferable, and examples thereof include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, and glycidyl methacrylate.

Moreover, when using the copolymer of ethylene, vinyl acetate, maleic acid, and / or maleic anhydride as said polymer, it is preferable that the vinyl acetate content of this copolymer is 10-50 weight%, More preferably, it is 14- 45 wt%. If the vinyl acetate content is lower than 10% by weight, sufficient crosslinking degree cannot be obtained in the case of crosslinking curing at high temperature. On the other hand, if the content exceeds 50% by weight, the strength and durability of the adhesive layer tend to be remarkably reduced. Moreover, it is preferable that the content rate of maleic acid and / or maleic anhydride of the said copolymer is 0.01-10 weight%, More preferably, it is 0.05-5 weight%. When the content of this maleic acid and / or maleic anhydride is lower than 0.01% by weight, the effect of improving the adhesive force is lowered, while when it exceeds 10% by weight, workability may be lowered.

When a copolymer of ethylene with an acrylate-based and / or methacrylate-based monomer and maleic acid and / or maleic anhydride is used as the polymer, the content of the acrylate-based monomer of the copolymer is 10 to 50% by weight. It is preferable that it is 14 to 45 weight% more preferably. If the content rate of the acrylate monomer is lower than 10% by weight, sufficient crosslinking degree cannot be obtained when crosslinking and curing at high temperature. On the other hand, if the content of the acrylate monomer exceeds 50% by weight, the strength and durability of the adhesive layer tend to be remarkably reduced. Moreover, it is preferable that the content rate of maleic acid and / or maleic anhydride of the said copolymer is 0.01-10 weight%, More preferably, it is 0.05-5 weight%. When the content of this maleic acid and / or maleic anhydride is lower than 0.01% by weight, the effect of improving the adhesive force is lowered, while when it exceeds 10% by weight, workability may be lowered. Moreover, the thing similar to what was mentioned above is mentioned as an acrylate type and / or a methacrylate type monomer.

When the ionomer resin (hereinafter referred to as "ethylene-methacrylic acid ionomer resin") in which the molecules of the ethylene-methacrylic acid copolymer are bonded to each other by metal ions as the polymer, the methacrylic acid content of the resin is It is preferable that it is 1-30 weight%, More preferably, it is 5-25 weight%. When the methacrylic acid content is lower than 1% by weight, the ion crosslinking effect is lowered, and further, the adhesion is lowered. On the other hand, when the methacrylic acid content is higher than 30% by weight, the workability may be remarkably lowered.

Examples of the metal ions used in the ethylene-methacrylic acid ionomer resin include metal cations such as sodium, zinc, magnesium, and lithium, and the degree of ionization by the metal ions is preferably 5 to 80%, more preferably. Preferably 7-70%. If ionization degree is less than 5%, transparency will fall remarkably, and if it exceeds 80%, the workability may fall remarkably.

An organic peroxide and / or a photosensitizer can be used for curing an anisotropic conductive film, but an organic peroxide is usually used when the curable adhesive is a thermosetting adhesive, and a photosensitizer is usually used when the curable adhesive is a photocurable adhesive.

As the organic peroxide added for curing the anisotropic conductive film, any one can be used as long as it decomposes at a temperature of 70 ° C. or higher to generate radicals. The decomposition temperature of a half-life of 10 hours is preferably 50 ° C. or higher, and the film forming temperature and preparation It is selected in consideration of conditions, curing (bonding) temperature, heat resistance of the adherend, and storage stability.

Organic peroxides that can be used include, for example, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, di-t-butyl Peroxide, t-butyl cumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumylperoxide, α, α'-bis (t-butylperoxyisopropyl) benzene , n-butyl-4,4'-bis (t-butylperoxy) valerate, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3 , 3,5-trimethylcyclohexane, t-butylperoxybenzoate, benzoyl peroxide, t-butylperoxy acetate, methyl ethyl ketone peroxide, 2,5-dimethylhexyl-2,5-bisperoxybenzoate , Butyl hydroperoxide, p-mentane hydroperoxide, p-chlorobenzoyl peroxide, hydroxybutyl peroxide, chlorohexanone peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, cumyl peroxy oct Eight, Scenic acid peroxide, acetyl peroxide, t-butylperoxy (2-ethylhexanoate), m-toluoyl peroxide, benzoyl peroxide, t-butylperoxy isobutylate, 2,4-dichlorobenzoyl Peroxide etc. are mentioned.

As an organic peroxide, at least 1 sort (s) is used individually or in mixture, Usually, 0.1-10 weight part is added and used with respect to 100 weight part of said polymers.

As a photosensitizer (photoinitiator) added for hardening of an anisotropic conductive film, a radical photoinitiator is used preferably. Among the radical photopolymerization initiators, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl sulfide, isopropyl thioxanthone, diethyl thioxanthone, 4- (diethylamino Ethyl benzoate, etc. can be used. Among the radical photopolymerization initiators, 2-hydroxy-2-methyl-1-phenylpropan-1-one as a benzoin ether, benzoylpropyl ether, benzyl dimethyl ketal, and α-hydroxyalkylphenone type as an intramolecular cleavage initiator , 1-hydroxycyclohexylphenyl ketone, alkylphenylglyoxylate, diethoxyacetphenone are also 2-methyl-1- [4- (methylthio) phenyl] -2-morpholi as the α-aminoalkylphenone type. Nopropanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 is also used as acylphosphine oxide. As a photosensitizer, at least 1 sort (s) of these is used individually or in mixture, Usually, 0.1-10 weight part is added and used with respect to 100 weight part of said polymers.

Examples of the silane coupling agent added as an adhesion promoter for the anisotropic conductive film include vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrichlorosilane, γ-mercaptopropyltri 1 type, or 2 or more types of mixtures, such as a methoxysilane, (gamma) -aminopropyl triethoxysilane, and N- (beta)-(aminoethyl)-(gamma) -aminopropyl trimethoxysilane, are used. The amount of these silane coupling agents added is usually 0.01 to 5 parts by weight with respect to 100 parts by weight of the polymer.

As an epoxy-group-containing compound added as an adhesion promoter of an anisotropic conductive film, triglycidyl tris (2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether, 1, 6- hexanediol diglycidyl Ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol (EO) 5 glycidyl ether, pt-butylphenyl glycidyl ether, adipic acid diglycidyl ester, Phthalic acid diglycidyl ester, glycidyl methacrylate, butyl glycidyl ether, etc. are mentioned. Moreover, the same effect can also be obtained by alloying the polymer containing an epoxy group. These epoxy group containing compounds are used as 1 type, or 2 or more types of mixtures, and the addition amount is 0.1-20 weight part normally with respect to 100 weight part of said polymers.

In order to improve or control the physical properties (mechanical properties, adhesion, optical properties, heat resistance, moist heat resistance, weather resistance, crosslinking rate, etc.) of the anisotropic conductive film, a compound having an acryloyl group, methacryloyl group or allyl group can be added. have. Compounds provided for this purpose are the most common acrylic acid or methacrylic acid derivatives, such as esters and amides thereof, and ester moieties include cyclohexyl groups, in addition to alkyl groups such as methyl, ethyl, dodecyl, stearyl, lauryl And tetrahydrofurfury, aminoethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 3-chloro-2-hydroxypropyl group and the like. In addition, esters with polyfunctional alcohols such as ethylene glycol, triethylene glycol, polypropylene glycol, polyethylene glycol, trimethylolpropane and pentaerythritol are also used in the same manner. Moreover, diacetone acrylamide is typical as an amide. Examples of the polyfunctional crosslinking aid include acrylic acid or methacrylic acid esters such as trimethylolpropane, pentaerythritol and glycerin, and compounds having allyl groups include triallyl cyanurate, triallyl isocyanurate, diallyl diallyl and isophthalic acid. Allyl, maleic acid diallyl, and the like.

These compounds are 1 type, or 2 or more types of mixtures, Usually, 0.1-50 weight part, Preferably 0.5-30 weight part is added with respect to 100 weight part of said polymers, and they are used. When it exceeds 50 weight part, the workability and film forming property at the time of adhesive preparation may fall.

Hydrocarbon resin can be added to an anisotropic conductive film in an adhesive agent for the purpose of improving processability, such as workability and joining. In this case, the hydrocarbon resin to be added may be either natural resin or synthetic resin. In natural resin systems, rosin, rosin derivatives, and terpene resins are preferably used. In rosin, rubber-based resins, tall oil-based resins, and weed-based resins can be used. As the rosin derivative, those obtained by hydrogenation, disproportionation, polymerization, esterification, and metal chlorides of rosin can be used. In the terpene-based resin, in addition to terpene-based resins such as α-pinene and β-pinene, terpene phenol resins can be used. In addition, as the other natural resin, it is also possible to use a terminal, a copal, a sherlock. On the other hand, in a synthetic resin system, petroleum resin, a phenol resin, and a xylene resin are used preferably. As the petroleum resin, an aliphatic petroleum resin, an aromatic petroleum resin, an alicyclic petroleum resin, a copolymerized petroleum resin, a hydrogenated petroleum resin, a pure monomer based petroleum resin, or a coumarone indene resin can be used. In phenolic resin, an alkyl phenol resin and a modified phenol resin can be used. In xylene resin, xylene resin and modified xylene resin can be used.

The addition amount of the hydrocarbon resin is appropriately selected, but is preferably 1 to 200 parts by weight, more preferably 5 to 150 parts by weight based on 100 parts by weight of the polymer. In addition to the above additives, anti-aging agents, ultraviolet absorbers, dyes, processing aids and the like may also be used in the present invention in a range that does not interfere with the object of the present invention.

As electroconductive particle used for an anisotropic conductive film, various things can be used as long as it is an electrically good conductor. For example, metal powders, such as copper, silver, and nickel, resin coated with such a metal, ceramic powder, etc. can be used. Moreover, there is no restriction | limiting in particular also about the shape, Arbitrary shapes, such as scale shape, resin shape, particle shape, and pellet shape, can be taken.

It is preferable that the compounding quantity of electroconductive particle is 0.1-15 volume% with respect to the said polymer, and particle diameter is 0.1-100 micrometers, It is preferable that it is 0.1-20 micrometers especially. By defining the blending amount and the particle diameter in this way, the conductive particles are not aggregated and annealed between adjacent circuits.

The anisotropic conductive film includes a crosslinking agent (organic peroxide and / or photosensitizer) generating radicals by heat or light described above as a main component, a crosslinking aid, a silane coupling agent, and an epoxy group-containing compound, if necessary. Are manufactured. That is, the anisotropic conductive film can be uniformly mixed with the above-mentioned additives and kneaded with an extruder, a roll, or the like, and then formed into a predetermined shape by a film forming method such as calender roll, T die extrusion, inflation, or the like.

Moreover, at the time of film forming, embossing may be carried out for the purpose of blocking prevention, and making it easy to crimp | bond with a to-be-adhered body. In order to bond the film obtained as mentioned above with a to-be-adhered body (polyimide copper foil etc.), the conventional method, for example, the bonding method by a hot press, the direct lamination method by an extruder, a calender, and the heat-compression method by a film laminator And the like can be used.

In addition, the components are uniformly dissolved in a solvent that does not affect the members at all, uniformly applied to the surface of the members, and temporarily adhered to other adherends (polyimide, copper foil, etc.), followed by heat or photocuring. You can.

As curing conditions of the anisotropic conductive film, in the case of thermosetting, it depends on the kind of organic peroxide to be used, but is usually 70 to 170 ° C, preferably 70 to 150 ° C, usually 10 seconds to 120 minutes, preferably 20 seconds to 60 minutes.

In the case of photocuring using a photosensitizer, many light emitting materials can be used as light sources in the ultraviolet to visible region. For example, ultra high pressure, high pressure, low pressure mercury lamp, chemical lamp, xenon lamp, halogen lamp, mercury halogen lamp, carbon Arc lamps, incandescent lamps, laser lights and the like.             

Irradiation time is not determined uniformly depending on the type of lamp and the intensity of the light source, but is about several tens to tens of minutes. Moreover, in order to accelerate hardening, a laminated body is previously heated at 40-120 degreeC, and it can also irradiate an ultraviolet-ray.

An anisotropic conductive film is obtained by adding an organic peroxide and / or a photosensitizer, a silane coupling agent, and an epoxy group containing compound together with electroconductive particle to the said polymer, and forming into a film.

This anisotropic conductive film has the following characteristics because an adhesive agent has the said polymer as a main component. (1) Repair property is good. (2) Transparency is good. (3) It is more stable and exhibits high adhesiveness than conventional products. (4) By using the film made of the said transparent polymer as a raw material, the light transmittance at the time of electrode positioning is good, and workability is favorable. (5) Although a conventional product such as epoxy is required to be heated to 150 ° C. or higher, curing adhesion can be performed at 100 ° C. or lower, and UV curing can also be performed. Therefore, curing adhesion at a lower temperature is also possible. (6) The epoxy- and phenol-based anisotropic conductive films conventionally used are not sticky, and thus the films are difficult to be temporarily fixed to the electrode by adhesive force, which is easy to stick to, and thus the workability is poor, but the anisotropic conductive film containing the polymer as a main component is temporarily fixed. Since adhesiveness at the time is high, workability | operativity is favorable.

Next, an Example and a comparative example are shown and the 1st invention of this invention is demonstrated more concretely. However, this invention is not limited by the following example.

<Example of 1st invention>

Example 1 (First Example: Particles)

As a base resin, the solution of 15 weight% of toluene was prepared using the polymer which substituted the hydroxyl group of saturated polyester with the methacryloxy group. 2 parts by weight of benzoyl peroxide, 5 parts by weight of a butylated melamine resin (manufactured by Dainippon Chemical Co., Ltd., Super Betkamin L125-60), and methacrylate phosphate (Kyoei Chemical Co., Ltd.) Note) 3 parts by weight of PIM), 20 parts by weight of polyethylene glycol diacrylate, and 0.5 parts by weight of γ-methacryloxypropyltrimethoxysilane were added and mixed well. 4 weight part of electroconductive particle (made by Nippon Chemical Co., Ltd., 16GNR 10.0MX, particle diameter: 5 micrometers) is mixed with respect to 100 weight part of base resins, cast at 70 degreeC with a roll coater, and 20 micrometers anisotropic conductive films Was prepared. The adhesive force of this anisotropic conductive film was 1.2 kg / inch when crimped | bonded at 140 degreeC for 10 second, and the conductive resistance was 2.5 ohms.

Next, the image display apparatus which has the display element of the structure shown in FIG. 1 was produced. A glass substrate was used as the transparent substrate, an epoxy plate was used for the counter substrate, and the anisotropic conductive film was used for the display electrode and the counter electrode. Adhesion of this anisotropic conductive film was performed by heating at 3 Mpa and 140 degreeC for 10 second. In addition, an insulating silicone resin was coated to a thickness of about 3 mu m to prevent adhesion and charge leakage on the surface of each electrode. As the negatively charged particles, an electrophotographic black polymeric toner (a spherical shape having an average particle diameter of 8 µm, a surface charge density of -50 µC / m 2, and a maximum value of surface potential 450 V after 0.3 second of the surface potential measurement) was used. As positively charged particles, titanium oxide was used as a white pigment, and quaternary ammonium salt-based compound was used as a charge control agent to produce polymerized particles of styrene acrylic resin (spherical shape with average particle diameter of 8 µm and surface charge density). +45 μC / m 2, the maximum value of surface potential 500 V after 0.3 seconds of the surface potential measurement. The charging of the particles was carried out by triboelectric charging by mixing equal amounts of both particles. The height of a partition was 200 micrometers, and the filling amount of the mixed particle was 70% of space.

When a direct current voltage of 200 V was applied such that the display electrode side was at high potential and the counter electrode side was at low potential, negatively charged particles were adhering to the display electrode side in an emergency, and the display element was displayed in white. Next, when the potential of the applied voltage was reversed, the negatively charged particles were attached to the counter electrode side in an emergency manner, and the display element was displayed in black.

As a result of measuring the response time for voltage application, it was 1 msec. In each display, voltage application was stopped and left for 1 day, but the display was maintained.

Next, the potential reversal of the applied voltage was repeated 10,000 times, but there was little change in the response speed.

Example 2 (First Example: Particles)

In the preparation of the anisotropic conductive film of Example 1, it carried out similarly to Example 1 except having used 20 weight part of neopentyl glycol dimethacrylates instead of 20 weight part of polyethyleneglycol diacrylates.

The adhesive force of the anisotropic conductive film was 1.1 kg / inch, the conductive resistance was 2.5?, And the performance of the image display device was the same as in Example 1.

Reference Example 1 (First Example: Particles)

The preparation of the anisotropic conductive film of Example 1 was carried out in the same manner as in Example 1 except that no butylated melamine resin and methacrylate phosphate were used.

The adhesive force of the anisotropic conductive film was 0.4 kg / inch, the conductive resistance was 2.9 Ω, and the performance of the image display device was the same as in Example 1.

Next, examples of using a classifier as a second embodiment of the first invention were examined. In addition, the physical property of the classification body in the Example and comparative example which concern on the following 1st invention and the function of the display apparatus were evaluated according to the following criteria.

(1) Average particle diameter and particle diameter distribution Span

Each classifier was put into the Mastersizer2000 (Malvern instruments Ltd.) measuring instrument, and the following value was calculated | required using the attached software (software which calculates particle diameter distribution and particle diameter based on a volume reference distribution).

Particle Diameter Distribution Span = (d (0.9) -d (0.1)) / d (0.5)

(However, d (0.5) is a numerical value in which 50% of the particulate matter constituting the classifier is larger than this, and 50% is smaller than this in diameter, and d (0.1) constitutes a classifier smaller than D (0.9) is the numerical value indicating the particle diameter of 90% of the particle material constituting the following classification body in μm)

Average particle diameter (micrometer): It is said d (0.5).

(2) The ratio of the appearance volume at the time of maximum floating of the fraction / the appearance volume at the time of not floating (V _max / V ₀ )

It measured by the method described in the text.             

(3) Time variation of the appearance volume of the fraction (V ₁₀ / V ₅ )

The apparent volume V ₅ (cm 3) after 5 minutes from the maximum suspension and the apparent volume V ₁₀ (cm 3) after 10 minutes from the maximum suspension were measured by the method described in the main text.

(4) Solvent insolubility of the fraction

The fraction was immersed in a methyl ethyl ketone solvent at 25 ° C. for 24 hours and dried at 100 ° C. for 5 hours to measure the weight. From the weight change before and after immersion, the solvent insoluble rate was measured according to the following formula.

Solvent insoluble rate (%) = (B / A) × 100

(A represents the weight before solvent dipping of the fraction, and B represents the weight after dipping the fraction at 25 ° C. for 24 hours in a methyl ethyl ketone solvent.)

(5) Evaluation of the display function of the display device

The voltage applied to the produced display device was raised, and the voltage at which the fractionated body moved to display was measured as the minimum drive voltage. When the specific example was shown, the voltage used as a threshold value was made into the minimum drive voltage as shown in FIG.

Next, black-white display was repeated by applying the voltage of the minimum drive voltage + 10V, and inverting electric potential.

Evaluation of the display function was measured using a reflection image density meter after the initial and 20000 repetitions for the contrast ratio and then left for 5 days. Here, the contrast ratio was taken as the contrast ratio = reflection density in black display / reflection density in white display. In addition, the contrast ratio of the initial stage was made into the retention rate for reference.

The response speed was obtained from the change of the output value using the photomultiplier tube.

Example 3 (Second Example: Sorting Body)

(Production of anisotropic conductive film)

As a base resin, the solution of 15 weight% of toluene was prepared using the polymer which substituted the hydroxyl group of saturated polyester with the methacryloxy group. 2 parts by weight of benzoylpropyl ether (photosensitizer), 5 parts by weight of butylated melamine resin (manufactured by Dainippon Chemical Co., Ltd., Superbecamine L125-60), and methacrylate phosphate (Kyoei Chemical Co., Ltd. product, PIM) 3 weight part, 20 weight part of polyethyleneglycol diacrylates, and 0.5 weight part of (gamma)-methacryloxypropyl trimethoxysilane were added, and it fully mixed. 4 weight part of electroconductive particle (made by Nippon Chemical Co., Ltd., 16GNR10.0MX, particle diameter: 5 micrometers) is mixed with respect to 100 weight part of base resins, cast at 70 degreeC with a roll coater, and 20 micrometers anisotropic conductive films Was prepared. The adhesive force which crimped | bonded this anisotropic conductive film at 140 degreeC for 10 second was 0.8 kg / inch, and conductive resistance was 2.7 ohms.

(Production of sorting body)

Next, two kinds of classifiers (classifier X, classifier Y) were produced.

The classifier X is first subjected to suspension polymerization using a methyl methacrylate monomer, TiO ₂ (20 phr), charge control agent Bontron E89 (manufactured by Orient Chemical Co., Ltd., 5 phr), initiator AIBN (0.5 phr), and then a classification apparatus. The particle diameters were aligned at. Next, an external additive A (silica H2000 / 4, manufactured by Wakka) and an external additive B (silica SS20, manufactured by Nippon Silica) were added to these particles using a hybridizer device (manufactured by Nara Machinery Co., Ltd.). The mixture was treated at 4800 revolutions for 5 minutes to fix the external additive on the surface of the polymerized particles, and adjusted to form a fraction.

The classifier Y is first subjected to suspension polymerization using a styrene monomer, an azo compound (5 phr), a charge control agent Bontron N07 (manufactured by Orient Chemical Co., Ltd., 5 phr), and an initiator AIBN (0.5 phr), followed by a classification apparatus. The particle diameter was aligned. Next, an external additive A (silica H2050, manufactured by Wakka) and an external additive B (silica SS20, manufactured by Nippon Silica) were added to these particles using a hybridizer device (manufactured by Nara Machinery Co., Ltd.). After 5 minutes of rotation, the external additive was fixed to the polymerized particle surface, and adjusted to form a fraction.

Physical properties of the classifier X and the classifier Y, i.e., the above-mentioned (1) average particle diameter and particle diameter distribution of the classifier, (2) the ratio of the external volume at the maximum suspension of the classifier to the external volume at the non-floating, (3 Table 1 shows the change in time (V ₁₀ / V ₅ ) and (4) the solvent insolubility of the classifier's appearance volume.

(Production of display device)

First, the board | substrate with an electrode which formed the partition mentioned above was produced.

A rib having a height of 250 µm was formed on a glass substrate on which an indium oxide electrode having a thickness of about 500 GPa was mounted by the anisotropic conductive film, and a partition wall having a striped convenient rib structure was formed.

The formation of the ribs was performed as follows. First, the paste is a glass powder obtained by melting, cooling, and pulverizing a mixture of SiO ₂ , Al ₂ O ₃ , B ₂ O _3, and ZnO as an inorganic powder, and preparing a thermosetting epoxy resin as a resin to obtain a viscosity of 15000 cps as a solvent. The prepared paste was produced.

Next, the paste was applied onto the entire surface of the substrate described above, heat cured at 150 ° C, and repeated application-curing to adjust the thickness (corresponding to the height of the partition wall) to 200 µm (sandblast method).

The dry photoresist was bonded to this, and the mask which formed the partition pattern of 50 micrometers of lines, 200 micrometers of space, and 250 micrometers of pitch by the exposure-etching was produced.

Next, the excess portion was removed by sandblasting so as to form a predetermined partition wall, and a desired stripe partition wall was formed.

Using an electrostatic coating machine, the fraction X was temporarily attached onto the glass substrate on which the previous indium oxide electrode was formed, and the fraction Y was temporarily attached on the other glass substrate, and adjusted with a spacer so as to have a distance of 120 µm. The two glass substrates were combined, the display substrate which bonded the glass substrate periphery with the epoxy adhesive, and enclosed the sorting body was produced. The mixing rate of the fraction X and the fraction Y was set to the same weight, and the filling rate between the glass substrates of these fractions was adjusted to be 60% by volume. Here, the gas of the space | gap part surrounding the fractional body between board | substrates was air of 35% RH of relative humidity.             

Table 1 shows the evaluation results of the display function of the obtained display device.

Example 4 (Second Example: Sort)

In Example 3, the display apparatus was produced similarly except having made the main material of the sorting body X and the sorting body Y into urethane (carbon for classifier Y is used together).

Table 1 shows the results of evaluation of the display function of the display device.

Example 5 (Second Example: Sort)

In Example 3, the display apparatus was produced in the same manner except having changed the addition amount of the initiator AIBN of the classifier X and the classifier Y into 0.1 phr.

Table 1 shows the evaluation results of the physical properties of the obtained fraction X and the fraction Y and the display function of the display device. Since the addition amount of the initiator AIBN was reduced, the solvent insolubility decreased, and the standing stability deteriorated slightly.

Example 6 (Second Example: Sort)

In Example 3, the display apparatus was similarly manufactured except having not performed classification after suspension polymerization at the time of preparation of the sorting body X and the sorting body Y.

Table 2 shows the evaluation results of the physical properties of the obtained fraction X and the fraction Y and the display function of the display device. Since it was not classified, the particle size distribution Span became large and durability fell slightly.

Example 7 (Second Example: Sort)

In Example 3, the display device was manufactured in the same manner except that the humidity of the air in the void portion surrounding the flow-dividing body between the substrates was 80% RH. Table 2 shows the evaluation results of the display visibility of the obtained display device. Due to the high humidity of the air in the voids, the durability deteriorated slightly.

Example 8 (Second Example: Sort)

In Example 3, a display device was manufactured in the same manner except that the partition wall was not formed. Table 2 shows the evaluation results of the display function of the obtained display device. Since there is no bulkhead, the durability deteriorates slightly.

Comparative Example 1 (Second Example: Classification)

In the preparation of the fraction X and the fraction Y of Example 3, the display device was manufactured in the same manner except that the processing conditions of the hybridizer were set at 4800 revolutions for 1 minute.

Table 3 shows the evaluation results of the physical properties of the obtained fraction X and the fraction Y and the display function of the display device. As a result of changing the processing conditions of the hybridizer, the state of the fractionated body deteriorated, so that the driving voltage became high, the durability deteriorated, and the response speed became slow.

Comparative Example 2 (Second Example: Sort)

In the preparation of the fraction X and the fraction Y of Example 3, the display device was manufactured in the same manner except that the processing conditions of the hybridizer were set at 4800 revolutions for 30 minutes.

Table 3 shows the evaluation results of the physical properties of the obtained classifier X and the classifier Y and the display function of the display device. As a result of changing the processing conditions of the hybridizer, the state of the fractionated body deteriorated, so that the driving voltage became high, the durability deteriorated, and the response speed became slow.

Comparative Example 3 (Second Example: Classification)

A display device was manufactured in the same manner as in Example 3, except that an electrophotographic toner commercially used for the classifier X and the classifier Y was used. Table 3 shows the evaluation results of the physical properties of the obtained fraction X and the fraction Y and the display function of the display device. As a result, the state of the fractionated body deteriorated, the driving voltage became high, the durability deteriorated, and the response speed became slow.

Example 9 (Second Example: Sort)

In the preparation of the anisotropic conductive film of Example 3, it carried out similarly to Example 3 except having used 20 weight part of neopentyl glycol dimethacrylates instead of 20 weight part of polyethyleneglycol diacrylates.

The adhesive force of the anisotropic conductive film was 0.7 kg / inch and the conductive resistance was 2.5?, And the evaluation result of the display function of the display device was the same as in Example 3.

Reference Example 2 (Second Example: Classification)

In the preparation of the anisotropic conductive film of Example 3, it carried out similarly to Example 3 except not using a butylated melamine resin and methacrylate phosphate.

The adhesive force of the anisotropic conductive film was 0.5 kg / inch, the conductive resistance was 2.8 Ω, and the evaluation result of the display function of the display device was the same as in Example 3.             

Table 1

Example 3 Example 4 Example 5 Taxonomy X (Material of the sorting body) Main material MAA monomer urethane MAA monomer TiO ₂ TiO ₂ TiO ₂   Initiator (phr) AIBN (0.5) AIBN (0.1)   Charge control agent Bontron 89 Bontron 89 Bontron 89 External additive A material Silica H2000 / 4 Silica H2000 / 4 Silica H2000 / 4          Diameter (nm) 20 20 20 External additive B material Silica SS20 Silica SS20 Silica SS20          Diameter (nm) 25 25 25 External additive attachment condition   Hybridizer time (min) 5 4 5 (Physical Properties of Classification) Particle Diameter (㎛) 3.3 5.2 4.1 Particle Diameter Distribution Span 1.6 1.9 1.8 V _max / V ₀ 3.1 2.5 2.6 V ₁₀ / V ₅ 0.91 0.88 0.87 Solvent insolubility (%) 92 92 48 Sort Y (Material of the sorting body) Main material Styrene Monomer urethane Styrene Monomer Azo compounds Carbon Azo compounds   Initiator (phr) AIBN (0.5) AIBN (0.1)   Charge control agent Bontron 07 Bontron 07 Bontron 07 External additive A material Silica H2050 Silica H2050 Silica H2050          Diameter (nm) 20 20 20 External additive B material Silica SS20 Silica SS20 Silica SS20          Diameter (nm) 25 25 25 External additive attachment condition   Hybridizer time (min) 5 7 5 (Physical Properties of Classification) Particle Diameter (㎛) 3.1 5.1 4.2 Particle Diameter Distribution Span 1.7 2.0 1.9 V _max / V ₀ 3.2 2.6 2.7 V ₁₀ / V ₅ 0.92 0.88 0.88 Solvent insolubility (%) 92 92 49 Relative humidity of air gap (%) 35 35 35 Bulkhead presence has exist has exist has exist (Evaluation of indication function) Drive voltage (V) 20 23 24 Initial contrast ratio 9.2 7.8 9.2 After 20000 times   Contrast Ratio 8.37 6.94 8.00   Retention rate (%) 91 89 87 5 days after leaving   Contrast Ratio 8.91 6.79 6.35   Retention rate (%) 98 87 69 Response speed (m / sec) 0.1 0.2 0.3

TABLE 2

Example 6 Example 7 Example 8 Taxonomy X (Material of the sorting body) Main material MAA monomer MAA monomer MAA monomer TiO ₂ TiO ₂ TiO ₂   Initiator (phr) AIBN (0.5) AIBN (0.5) AIBN (0.1)   Charge control agent Bontron 89 Bontron 89 Bontron 89 External additive A material Silica H2000 / 4 Silica H2000 / 4 Silica H2000 / 4          Diameter (nm) 20 20 20 External additive B material Silica SS20 Silica SS20 Silica SS20          Diameter (nm) 25 25 25 External additive attachment condition   Hybridizer time (min) 5 5 5 (Physical Properties of Classification) Particle Diameter (㎛) 4.2 3.3 3.3 Particle Diameter Distribution Span 5.1 1.6 1.6 V _max / V ₀ 2.1 3.1 3.1 V ₁₀ / V ₅ 0.81 0.91 0.91 Solvent insolubility (%) 91 92 92 Sort Y (Material of the sorting body) Main material Styrene Monomer Styrene Monomer Styrene Monomer Azo compounds Azo compounds Azo compounds   Initiator (phr) AIBN (0.5) AIBN (0.5) AIBN (0.5)   Charge control agent Bontron 07 Bontron 07 Bontron 07 External additive A material Silica H2050 Silica H2050 Silica H2050          Diameter (nm) 20 20 20 External additive B material Silica SS20 Silica SS20 Silica SS20          Diameter (nm) 25 25 25 External additive attachment condition   Hybridizer time (min) 5 5 5 (Physical Properties of Classification) Particle Diameter (㎛) 4.3 3.1 3.1 Particle Diameter Distribution Span 5.2 1.7 1.7 V _max / V ₀ 2.0 3.2 3.2 V ₁₀ / V ₅ 0.80 0.92 0.92 Solvent insolubility (%) 91 92 92 Relative humidity of air gap (%) 35 35 35 Bulkhead presence has exist has exist has exist (Evaluation of indication function) Drive voltage (V) 42 38 21 Initial contrast ratio 9.0 8.8 9.2 After 20000 times   Contrast Ratio 7.38 7.04 7.73   Retention rate (%) 82 80 84 5 days after leaving   Contrast Ratio 7.20 6.07 7.36   Retention rate (%) 70 69 80 Response speed (m / sec) 1.1 2.1 0.2

TABLE 3

Comparative Example 1 Comparative Example 2 Comparative Example 3 Taxonomy X (Material of the sorting body) Main material MAA monomer MAA monomer Commercially available toner TiO ₂ TiO ₂ (yellow)   Initiator (phr) AIBN (0.5) AIBN (0.5)   Charge control agent Bontron 89 Bontron 89 External additive A material Silica H2000 / 4 Silica H2000 / 4          Diameter (nm) 20 20 External additive B material Silica SS20 Silica SS20          Diameter (nm) 25 25 External additive attachment condition   Hybridizer time (min) One 30 (Physical Properties of Classification) Particle Diameter (㎛) 4.7 4.9 7.2 Particle Diameter Distribution Span 2.2 1.8 1.8 V _max / V ₀ 1.2 1.2 1.2 V ₁₀ / V ₅ 0.69 0.58 0.68 Solvent insolubility (%) 91 92 90 Sort Y (Material of the sorting body) Main material Styrene Monomer Styrene Monomer Commercially available toner Azo compounds Azo compounds (black)   Initiator (phr) AIBN (0.5) AIBN (0.5)   Charge control agent Bontron 07 Bontron 07 External additive A material Silica H2050 Silica H2050          Diameter (nm) 20 20 External additive B material Silica SS20 Silica SS20          Diameter (nm) 25 25 External additive attachment condition   Hybridizer time (min) One 30 (Physical Properties of Classification) Particle Diameter (㎛) 4.8 5.0 6.9 Particle Diameter Distribution Span 2.2 1.8 1.8 V _max / V ₀ 1.2 1.2 1.2 V ₁₀ / V ₅ 0.69 0.59 0.70 Solvent insolubility (%) 92 90 90 Relative humidity of air gap (%) 35 35 35 Bulkhead presence none has exist has exist (Evaluation of indication function) Drive voltage (V) 95 88 125 Initial contrast ratio 8.8 9 6.7 After 20000 times   Contrast Ratio 4.93 4.59 3.35   Retention rate (%) 56 51 50 5 days after leaving   Contrast Ratio 4.40 4.32 3.15   Retention rate (%) 70 48 47 Response speed (m / sec) 11.0 8.1 8.9

(About 2nd invention)

A feature of the image display device according to the second aspect of the present invention is that the image display panel and the optical function member are provided, and the image display panel and the optical function member are integrated through a transparent elastic layer.

The optical function member integrated display device is deformed when pressure is applied to the display unit, and the screen is blurred, particularly when the display unit is an image display panel. For this reason, in the conventional optical function member integrated display device, the optical function member and a display part are connected through a spacer, and the space | gap of about 0.4 mm is formed between members, and pressure is not applied to a display part.

However, such voids cause reflection scattering and absorption of light, which drastically lowers the contrast ratio, which is important as a display, and causes problems such as deterioration of visibility, parallax at the time of input, and shadow of display. It is causing.

This invention is made | formed in view of the said situation, is connected without forming a space | gap between optical function members, such as an anti-reflective process glass, and a display panel, and is excellent in light transmittance, and the fall of contrast ratio is suppressed as much as possible, An optical function member integrated display device having excellent display performance is provided.

As the optical function member in the image display device of the present invention, a known one can be used. For example, a light-transmissive antireflective glass, an antireflection treatment film, an antistatic glass, an antistatic film, an electromagnetic shielding material, a near infrared absorbing film , Color filters, touch panels, shields for mobile phones, and the like. Polycarbonate, glass, an acrylic resin, etc. are mentioned as a material. These optical function members can be suitably selected and used according to the use of the image display apparatus of this invention.

As for the transparent elastic layer in the image display apparatus of this invention, what is necessary is just to optimize refractive index as mentioned later, For example, synthetic rubbers, such as a polyisoprene and polybutadiene, olefin elastomers, such as EVA, a polyurethane elastomer, polyvinyl Butyral, vinyl chloride-based elastomers, styrene-based elastomers such as SBS and SIS, acrylic resins, silicone polymers, and the like, and the like, and in particular, the use of acrylic resins is recommended.

Although it is recommended that the transparent elastic layer in the image display apparatus of this invention be the said material as a main material, it can further mix | blend other materials together as needed. As a material that can be used in combination, organic peroxides, photosensitizers, plasticizers, adhesion promoters, hydrocarbon resins, anti-aging agents (polymerization inhibitors, antioxidants, ultraviolet absorbers, etc.) and other inorganic or organic fillers may be added. have. Moreover, an effective amount of the conventionally well-known flame retardant of inorganic type, halogen type, and phosphorus type can also be added. In this case, it can mix and optimize variously in the ratio of 0.1-50 mass parts normally with respect to 100 mass parts of said main materials.

The transparent elastic layer can be formed by applying the material directly to a member or by forming a film into a film by a known film forming method such as calender, roll, T die extrusion, or inflation. In this case, the thickness of the transparent elastic layer is usually 0.01 to 5 mm, particularly preferably 0.05 to 3 mm.             

In the image display device of the present invention, when the refractive index of the transparent elastic layer is n ₀ , the refractive index of the optical function member is n ₁ , and the refractive index of the transparent substrate of the reversible image display panel is n ₂ , the transparent elastic layer It is necessary that the refractive index n ₀ be each optimized for the refractive index n ₁ of the optical function member and the refractive index n ₂ of the transparent substrate. Specifically, the absolute value of the difference between n ₀ and n ₁ is preferably 0.2 or less, in particular 0.1 or less, and the absolute value of the difference between n ₀ and n ₂ is preferably 0.2 or less, particularly 0.1 or less.

From the effect by the optimization of these refractive indices, it is excellent in light transmittance, the fall of contrast ratio is suppressed, and the outstanding display property can be reliably obtained. If the difference between these refractive indices is too large, the reflectivity at the interface becomes large and the visibility is lowered.

In the present invention, the transparent elastic layer has a strain (ε ₀ ) of 5% at 25 ° C., which is a stress relaxation property, and G ₀ is 6.5 when the initial value (after 0.05 seconds) of the stress relaxation modulus is G ₀ . It is preferable that it is x10 <^6> Pa or less, especially 5.5x10 <^6> Pa or less. It is preferable that this minimum is 4.0 * 10 <^6> Pa or more.

By setting the initial value G ₀ of the relaxation elastic modulus in this range, even if the surface of the protective plate or the like is pressed, it is possible to reliably avoid generation of deformation, color deviation and the like of the display unit without affecting the display unit. When it exceeds the said range, deformation of a display part cannot be avoided and it will become easy to crack. If it is less than the lower limit, the mechanical strength after joining may be insufficient, and heat resistance may fall.

In the present invention, the transparent elastic layer is a relation between the stress relaxation modulus (G) and the time (t (second)) obtained from the damping curve of the stress relaxation modulus,

1 nG (t) =-t / τ + 1 nG ₀

It is preferable that the stress relaxation time (tau) computed by is 17 second or less, especially 12 second or less, and it is preferable that it is 7 second or more as a minimum.

By optimizing the stress relaxation time in this manner, it is possible to reliably alleviate the deformation occurring in the display portion, and to prevent the occurrence of color deviation of the display screen of the image display device. In this case, when the relaxation time exceeds the above range, static deformation may not be relaxed, and color deviation may easily occur.

In order to obtain the optical function member integrated display device of the present invention, the image display panel and the optical function member may be integrated through a transparent elastic layer, and the manufacturing method thereof is not particularly limited. For example, a method of forming a transparent elastic layer in advance by the above method, applying a predetermined adhesive material and bonding, and applying the material of the transparent elastic layer to either side of the optical function member or the image display panel in a molten state, and then the other The method of joining and integrating a member, etc. can be employ | adopted. As the method of integrating, a known method such as a vacuum press method or a nip roll method can be used. When air remains at the interface, a method of applying pressure heating by using a liquid adhesive or an autoclave device or the like can be adopted. .             

Next, an Example and a comparative example are shown and the 2nd invention of this invention is demonstrated more concretely. However, the present invention is not limited by the following examples.

<Example of 2nd invention>

Reference Example 11 (First Example: Particles)

An image display panel having a display element having the configuration shown in FIG. 3 was produced. The glass substrate was used as a transparent substrate, the epoxy board was used for the opposing board | substrate, and the display electrode and the counter electrode were made into the copper electrode. An insulating silicone resin was coated to a thickness of about 3 mu m to prevent adhesion and charge leakage on the surface of each electrode. As the negatively charged particles, an electrophotographic black polymeric toner (a sphere having an average particle diameter of 8 µm, a surface charge density of -50 µC / m 2, and a maximum value of surface potential 450 V after 0.3 second of the surface potential measurement) was used. As positively charged particles, titanium oxide was used as a white pigment, and quaternary ammonium salt-based compound was used as a charge control agent, thereby producing polymerized particles of styrene acrylic resin (a spherical particle having an average particle diameter of 8 µm and a surface charge density of +45 µC). / M 2, the maximum value of the surface potential 500 V after 0.3 seconds of the surface potential measurement. The charging of the particles was carried out by frictional charging by mixing equal amounts of both particles. The height of a partition was 200 micrometers, and the filling amount of the mixed particle was 70% of space.

When a direct current voltage of 200 V was applied such that the display electrode side was at high potential and the counter electrode side was at low potential, negatively charged particles were adhering to the display electrode side in an emergency, and the display element was displayed in white. Next, when the potential of the applied voltage was reversed, the negatively charged particles were attached to the counter electrode side in an emergency, and the display element was displayed in black.             

As a result of measuring the response time for voltage application, it was 1 msec. In each display, voltage application was stopped and left for 1 day, but the display was maintained. Next, the potential inversion of voltage application was repeated 10,000 times, but there was little change in the response speed.

About the amount of transmitted light, the light reflected by irradiating light with light from the surface of the obtained image display panel is measured by a luminance meter, and the amount of reflected light at this time is made into the reference value (100%).

Example 11 (First Example: Particles)

As an image display panel obtained in Reference Example 11, a glass transparent substrate having a refractive index n ₂ = 1.49 was provided on both sides of the front and back. An acrylic adhesive material (manufactured by Soken Chemical Co., Ltd., trade name SK Dyne 1831) is applied as a transparent elastic layer on a predetermined transparent substrate on the display surface, and a polycarbonate protective window material (thickness 1.5) is provided on this chart surface as an optical function member. ㎜, the refractive index n and the bond ₁ = 1.59), to prepare the optically functional members integrated image display device.

Formed of a transparent elastic layer 0.5㎜ thickness, refractive index _{n 0 = 1.49, G 0 =} 5.5 × 10 6 ㎩, the stress relaxation time was 12 seconds.

The amount of transmitted light in the optical function member integrated image display device was 95% using the reflected light amount in Reference Example 11 as the reference value (100%).

Comparative Example 11 (2nd Example: Particles)

On the transparent substrate of the image display panel obtained in Reference Example 11, the same polycarbonate protective window member as in Example 11 was bonded through a spacer (height 0.5 mm) in a conventional manner, and the transparent substrate and the polycarbonate protective window member of the image display panel The optical function member integrated image display apparatus which provided the air window of thickness 0.5mm between was produced. The amount of transmitted light in the optical function member integrated image display device was 87% based on the amount of reflected light in Reference Example 11 as a reference value (100%).

Next, examples of using a classifier as a second embodiment of the second invention were examined. In addition, the physical property of the classifier in the Example and comparative example which concern on the following 2nd invention, and the function of the display apparatus were evaluated according to the same criteria as the example demonstrated by the example of 1st invention.

Reference Example 12 (Second Example: Classification)

(Production of sorting body)

The following two kinds of classification bodies (classification X and classification Y) were produced.

The classifier X is first subjected to suspension polymerization using a methyl methacrylate monomer, TiO ₂ (20 phr), charge control agent Bontron E89 (manufactured by Orient Chemical Co., Ltd., 5 phr), initiator AIBN (0.5 phr), and then classified. The particle diameter was aligned with the device. Next, an external additive A (silica H2000 / 4, manufactured by Wakka) and an external additive B (silica SS20, manufactured by Nippon Silica) were introduced into these particles using a hybridizer device (manufactured by Nara Machinery Co., Ltd.). 5 minutes at 4800 revolutions, the external additive was fixed on the surface of the polymerized particles, and adjusted to a fraction.

The classifier Y is first subjected to suspension polymerization using a styrene monomer, an azo compound (5 phr), a charge control agent Bontron N07 (manufactured by Orient Chemical Co., Ltd., 5 phr), and an initiator AIBN (0.5 phr), followed by a classification apparatus. The particle diameter was aligned. Next, an external additive A (silica H2050, manufactured by Wakka) and an external additive B (silica SS20, manufactured by Nippon Silica) were added to these particles using a hybridizer device (manufactured by Nara Machinery Co., Ltd.). After 5 minutes of rotation, the external additive was immobilized on the surface of the polymerized particles to prepare a fraction.

Physical properties of the classifier X and the classifier Y, i.e., the average particle diameter and particle diameter distribution Span of the above-mentioned (1) classifier, and (2) the ratio of the external volume at the maximum suspension of the classifier to the external volume at the non-floating (V _max / V ₀ ), (3) Time change (V ₁₀ / V ₅ ) of the appearance volume of the fraction, and (4) The solvent insolubility of the fraction is shown below.

Taxonomy X Sort Y Particle Diameter (㎛) 3.3 3.1 Particle Diameter Distribution 1.6 1.7 V _max / V ₀ 3.1 3.2 V ₁₀ / V ₅ 0.91 0.92 Solvent insoluble rate (%) 92 92

(Production of image display board)

First, the board | substrate with an electrode in which the partition mentioned later was formed was produced.

On the glass substrate in which the indium oxide electrode of about 500 micrometers in thickness was formed, the rib of 250 micrometers in height was made, and the partition of the stripe-shaped convenient rib structure was formed.

The formation of the ribs was performed as follows. First, the paste is a glass powder obtained by melting, cooling and pulverizing a mixture of SiO ₂ , Al ₂ O ₃ , B ₂ O _3, and ZnO as an inorganic powder, and preparing a thermosetting epoxy resin as a resin, and having a viscosity of 15000 cps as a solvent. The paste prepared as described above was produced.

Next, the paste was applied to the entire surface of the substrate described above, heated and cured at 150 ° C., and repeated application-curing to adjust the thickness (corresponding to the height of the partition wall) to 200 μm (sandblasting method).

The dry photoresist was bonded to this, and the mask which formed the partition pattern of 50 micrometers of lines, 200 micrometers of space, and 250 micrometers of pitch by the exposure-etching was produced.

Next, the excess portion was removed by sandblasting so as to form a predetermined partition wall, and a partition wall having a desired stripe shape was formed.

Using an electrostatic coating machine, the fraction X is temporarily attached onto the glass substrate on which the former indium oxide electrode is formed, and the fraction Y is temporarily attached to the other glass substrate, and adjusted to a spacer so that the interval is 120 µm. Then, both glass substrates were bonded together, the periphery of the glass substrate was bonded by the epoxy adhesive, and the image display panel which enclosed the classification body was produced. The mixing rate of the fraction X and the fraction Y was set to the same weight, and the filling ratio between these fractions between the glass substrates was adjusted so that it might be 60 volume%. Here, the gas of the space | gap part surrounding the fractional body between board | substrates was air of 35% RH of relative humidity.             

As for the display function of the obtained image display apparatus, the minimum drive voltage was 20V, the initial contrast ratio of the reflection density in black display / reflection density in white display was 9.2, and the response speed was 0.1 msec.

Moreover, the contrast ratio after 20000 times was 8.37 (keeping ratio 91%), and the contrast ratio after 5 days left was 8.19 (keeping ratio 89%).

Regarding the amount of transmitted light, light is emitted by the light from the surface of the obtained image display panel, the reflected light is measured by a luminance meter, and the amount of reflected light at this time is taken as the reference value (100%).

Example 12 (Second Example: Sort)

An image display panel obtained in Reference Example as a display and a display, a glass transparent substrate having a refractive index n ₂ = 1.49 was used having a front and back faces. An acrylic adhesive material (manufactured by Soken Chemical Co., Ltd., product name SK Dyne 1831) is applied as a transparent elastic layer on one of the display substrates on a predetermined transparent surface, and a polycarbonate protective window material (1.5 mm in thickness) as an optical function member on the coated surface. And refractive index n ₁ = 1.59) were bonded together to produce an optical function member-integrated image display device.

The formed transparent elastic layer had a thickness of 0.5 mm, refractive index n ₀ = 1.49, G ₀ = 5.5 × 10 ⁶ Pa, and stress relaxation time was 12 seconds.

The amount of transmitted light in the optical function member integrated image display device was 95% using the reflected light amount in Reference Example 12 as a reference value (100%).             

Comparative Example 12 (Second Example: Sort)

On the transparent substrate of the image display plate obtained in Reference Example 12, the same polycarbonate protective window member as in Example 12 was bonded through a spacer (height 0.5 mm) in a conventional manner, and between the transparent substrate of the image display panel and the polycarbonate protective window member. The optical function member integrated image display apparatus in which the air layer of 0.5 mm in thickness was formed was produced. The amount of transmitted light in the optical function member integrated image display device was 87% based on the amount of reflected light of Reference Example 12 as a reference value (100%).

(About 3rd invention)

A feature of the image display device according to the third aspect of the present invention is that an antireflection layer having two or more layers having different refractive indices is formed on the surface of the transparent substrate, that is, on the outer surface or the inner surface, or the outer surface and the inner surface.

The antireflection layer is formed by alternately stacking layers having different refractive indices, that is, high and low refractive materials, to suppress external light reflection and to transmit light having a specific wavelength, thereby displaying a clear image.

The antireflection layer prevents reflection of light of 380 to 780 nm, preferably has a light reflectance of 10% or less, and particularly preferably 8% or less.

It is preferable to form each by sputtering using conductive silicon carbide as a target for the low refractive layer of this antireflection layer and conductive titanium oxide as a target for the high refractive layer.

That is, by using conductive silicon carbide as a target, a high force can be applied without being damaged. In addition, the film forming speed can be increased by using conductive titanium oxide and conductive silicon carbide as targets.

Further, the low refractive layer is a silicon compound represented by a group consisting of SiC _x , SiO _x , SiN _x , SiC _x O _y , SiC _x N _y , SiO _x N _y , SiC _x O _y N _z , in particular SiC _x O _y (Wherein X is 0.1 to 3, preferably 0.5 to 2.5, y is 0.1 to 3, preferably 0.5 to 2.5, z is 0.1 to 3, preferably 0.5 to 2.5), and the high refractive layer is TiO _t (T is preferably 0.1 to 3, preferably 0.5 to 2.5).

The lamination thickness and the number of laminations of the low refractive index layer and the high refractive layer are arbitrarily designed to have the required properties as the antireflection film, for example, the first layer SiC _x O _y 15 nm, the second layer TiO _t 30 nm, the third layer 125 nm, By laminating the fourth layer TiO _t 94.5 nm (wherein x is 0.1 to 3, y is 0.1 to 3 and t is 0.1 to 3), the characteristics of the antireflection film of visible light are obtained. Thus, the thickness of each layer does not need to be the same, and is designed arbitrarily according to the characteristic requested | required.

The sputtering method is preferably a magnetron sputtering method, in particular a dual cathode magnetron sputtering method.

Moreover, the method in which the low refractive layer is formed into a film under a mixed gas atmosphere of an inert gas and a reactive gas is preferable, and a gas containing oxygen in the molecule is used as the reactive gas.

At the time of sputtering, the carbon compound needs to be gasified to be exhausted out of the vacuum chamber so that the carbon compound is not deposited in the vacuum chamber and is not mixed in the transparent conductive film during film formation.

Sputtering conditions such as the type of supply gas, flow rate, pressure, and supply power can be arbitrarily set in consideration of the target to be used, the film forming speed, and the like.

In addition, the conductive titanium oxide target generally means a target having a volume resistivity of 2 × 10 ⁻¹ Ω · cm or less, and the conductive silicon carbide target generally means a target having a volume resistivity of 2 × 10 ⁻² Ω · cm or less. The film forming speed is increased by using the conductive titanium oxide target or the conductive silicon carbide target.

As the silicon carbide target, one obtained by sintering a mixture of silicon carbide powder and a nonmetallic sintering aid (coal tar pitch, phenol resin, furan resin, epoxy resin, glucose, sucrose, cellulose, starch, etc.) is used, and the density of the silicon carbide target is 2.9. It is preferable that it is g / cm <3> or more. With such a high density and uniform target, stable discharge can be performed at high input during sputtering film formation, and the film forming speed can be increased.

By using the silicon carbide target, there is an advantage that the carbon compound produced from silicon carbide is gasified in the vacuum chamber and exhausted out of the vacuum chamber, so that no carbon compound is deposited in the vacuum chamber and is not incorporated into the antireflection film in the film formation.

Next, an Example and a comparative example are shown and the 3rd invention of this invention is demonstrated more concretely. However, the present invention is not limited by the following examples.

<Example of 3rd invention>             

Example 21 (First Example: Particles)

(Production of Anti-reflective Film)

On the glass substrate, an antireflection layer formed by alternately laminating two low refractive index layers targeting conductive silicon carbide and two high refractive index layers targeting conductive oxide oxide was formed.

For film formation of the low refractive index layer, a magnetron sputtering apparatus was used as the sputtering apparatus, and the target material was made of conductive silicon carbide (Bridgestone Co., Ltd., resistance value 2 × 10 ⁻² Ω · cm), and the supply gas was argon 10 cc / min. And sputtering conditions of oxygen gas 3 cc / min, pressure 5 mTorr, and supply power 1.2 kPa.

For film formation of the high refractive index layer, a magnetron sputtering apparatus was used as the sputtering apparatus, and the target material was conductive titanium oxide (manufactured by Asahi Glass Co., Ltd., resistance value 2 × 10 ⁻¹ Ω · cm), and the supply gas was argon 10cc / min, a pressure of 5 mTorr, and a sputtering condition of 1.2 kW of supply power.

The composition, layer thickness, and film forming time of the obtained antireflection layer are shown below.

Film Material Film Thickness (nm) Film Production Time (min)

1st layer SiC _0.8 O _1.2 15.0 0.63

2nd layer TiO _1.9 30.0 0.83

3rd layer SiC _0.8 O _1.2 125.0 5.21

4th layer TiO _1.9               94.5 2.63

Total Production Time 9.29

The optical performance of the produced antireflection layer is shown in FIG.

(Production of an image display device)

The image display apparatus was produced using the glass substrate which has the said antireflection layer. An epoxy board was used for the counter substrate, and the display electrode and the counter electrode were copper electrodes. Insulating silicone resin was coated to a thickness of about 3 mu m to prevent adhesion and charge leakage on each electrode surface. As the negatively charged particles, an electrophotographic black polymeric toner (a sphere having an average particle diameter of 8 µm, a surface charge density of -50 µC / m 2, and a maximum value of surface potential 450 V after 0.3 second of the surface potential measurement) was used. As positively charged particles, titanium oxide was used as a white pigment, and quaternary ammonium salt-based compound was used as a charge control agent to prepare polymerized particles of styrene acrylic resin (spherical with an average particle diameter of 8 µm, surface charge density +45 µC / m 2, The maximum value of surface potential 500V after 0.3 second of said surface potential measurement). The charging of the particles was carried out by frictional charging with equal mixing of both particles. The height of a partition was 200 micrometers, and the filling amount of the mixed particle was 70% of space.

When a 200 V DC power supply is applied such that the display electrode side is at a high potential and the opposite electrode side is at a low potential, negatively charged particles are attached to the display electrode side in an emergency manner, and the display element is displayed in white. Next, when the potential of the applied voltage is reversed, the negatively charged particles are attached to the counter electrode side in an emergency manner, and the display element is displayed in black.

It was 1 msec when the response time to voltage application was measured. In each display, voltage application was stopped and left for 1 day, but the display was maintained.

Next, although the potential inversion of voltage application was repeated 10,000 times, the response speed hardly changed.

Reference Example 21 (First Example: Particles)

In Example 21, an antireflection layer formed by alternately laminating two low refractive index layers targeting silicon and two high refractive index layers targeting titanium was formed on the glass substrate.

The film formation of the low refractive index layer was performed using a magnetron sputtering apparatus as a sputtering apparatus, and the target material was Si, and the supply gas was sputtered under argon 5cc / min, oxygen gas 5cc / min, pressure 5mTorr, and supply power 1.2 kW. .

The film of the high refractive index layer was formed using a magnetron sputtering apparatus as a sputtering apparatus, and the target material was Ti, and the supply gas was sputtered under argon 5cc / min, oxygen gas 5cc / min, pressure 5mTorr, and supply power 1.2 kW. .

The layer thicknesses of the low refractive index layer and the high refractive index layer were the same as in Example 21. The film forming time was 7.50 minutes for the first layer, 10.00 minutes for the second layer, 62.50 minutes for the third layer, and 31.50 minutes for the fourth layer, and the total film forming time was 111.50 minutes.

Example 21 shows that the image display device of the present invention is fast in response and excellent in stability, and has a very low reflectance of visible light in the antireflection layer, whereby a clear image is obtained.

In addition, in Example 21, the film forming time takes about 2 hours, whereas in Example 21, four antireflection layers were obtained in about nine minutes and a half, and the conductive silicon carbide was targeted at the low refractive layer, and the conductive film was formed at the high refractive layer. By forming sputtering with titanium oxide as a target, it can be seen that the antireflection layer can be formed in a very short time.

Next, as an example of the second embodiment of the third invention, an example using a classifier was examined. In addition, the physical property of the classifier in the Example and comparative example which concern on the following 3rd invention, and the function of the display apparatus were evaluated according to the same criteria as the example demonstrated in the example of 1st invention.

Example 22 (Second Example: Sort)

(Production of Anti-reflective Film)

On the glass substrate, an antireflection layer formed by alternately laminating two low refractive index layers targeting conductive silicon carbide and two high refractive index layers targeting conductive oxide oxide was formed.

For film formation of the low refractive index layer, a magnetron sputtering apparatus was used as the sputtering apparatus, and the target material was made of conductive silicon carbide (made by Bridgestone Co., Ltd., resistance value 2 × 10 ⁻² Ω · cm), and the supply gas was argon 10 cc / min. And sputtering conditions of oxygen gas 3 cc / min, pressure 5 mTorr, and supply power 1.2 kPa.

For the film formation of the high refractive index layer, a magnetron sputtering apparatus was used as the sputtering apparatus, the target material was conductive titanium oxide (manufactured by Asahi Glass Co., Ltd., resistance value 2 × 10 ⁻¹ Ω · cm), and the supply gas was argon 10cc / min, a pressure of 5 mTorr, and a sputtering condition of a power supply of l.2 kPa.

The composition, layer thickness, and film forming time of the obtained antireflection layer are shown below.

Film Material Film Thickness (nm) Film Production Time (min)

1st layer SiC _0.8 O _1.2 15.0 0.63

2nd layer TiO _1.9 30.0 0.83

3rd layer SiC _0.8 O _1.2 125.0 5.21

4th layer TiO _1.9              94.5 2.63

Total Production Time 9.29

The optical performance of the produced antireflection layer is shown in FIG.

(Production of sorting body)

Next, two kinds of classification bodies (classification X, classification Y) were produced.

The classifier X is first subjected to suspension polymerization using a methyl methacrylate monomer, TiO ₂ (20 phr), charge control agent Bontron E89 (manufactured by Orient Chemical Co., Ltd., 5 phr), initiator AIBN (0.5 phr), and then classified. The apparatus was used to make the particle diameter uniform. Next, by using a hybridizer device (manufactured by Nara Machinery Co., Ltd.), external particles A (silica H2000 / 4, manufactured by Wakka) and external additive B (silica SS20, manufactured by Nippon Silica) were added to these particles. The mixture was charged and treated at 4800 revolutions for 5 minutes, and the external additive was immobilized on the polymerized particle surface to prepare a fraction.

The classifier Y is first subjected to suspension polymerization using a styrene monomer, an azo compound (5 phr), a charge control agent Bontron N07 (manufactured by Orient Chemical Co., Ltd., 5 phr), an initiator AIBN (0.5 phr), and then a classification apparatus. To make the particle diameter uniform. Next, an external additive A (silica H2050, manufactured by Wakka) and an external additive B (silica SS20, manufactured by Nippon Silica) were added to these particles using a hybridizer device (manufactured by Nara Machinery Co., Ltd.). After 5 minutes of rotation, the external additive was immobilized on the surface of the polymerized particles to prepare a fraction.

Physical properties of the classifier X and the classifier Y, i.e., the above-mentioned (1) average particle diameter and particle diameter distribution of the classifier, (2) the ratio of the external volume at the maximum flotation of the classifier to the external volume at the no-float, (3 The change in time (V ₁₀ / V ₅ ) and (4) the solvent insolubility of the classifier's appearance volume are shown below.

Taxonomy X Taxonomy Y

Particle Diameter (㎛) 3.3 3.1

Particle Diameter Distribution Span 1.6 1.7

V _max / V ₀ 3.1 3.2

V ₁₀ / V ₅ 0.91 0.92

Solvent insolubility (%) 92 92

(Production of an image display device)

The image display apparatus was produced using the glass substrate which has the said antireflection layer.

First, the board | substrate with an electrode in which the partition described below was formed was produced. On the glass substrate having the antireflection layer on which an indium oxide electrode having a thickness of about 500 kPa was formed, ribs having a height of 250 µm were formed to form partition walls having a stripe-shaped convenient rib structure.

The rib was formed as follows. First, the paste is a glass powder obtained by melting, cooling, and pulverizing a mixture of SiO ₂ , Al ₂ O ₃ , B ₂ O _3, and ZnO as an inorganic powder, and preparing a thermosetting epoxy resin as a resin, and using a solvent to obtain a viscosity of 15000 cps. The paste prepared to be was produced.

Next, the paste was applied on the entire surface of the substrate described above, heat cured at 150 ° C., and repeated application-curing to prepare a thickness (corresponding to the height of the partition wall) to 200 μm (sandblasting method).

The dry photoresist was bonded to this, and the mask which formed the partition pattern of 50 micrometers of lines, 200 micrometers of spaces, and 250 micrometers of pitches by the exposure-etching was produced.

Subsequently, an extra portion was removed by sandblasting so as to form a predetermined partition wall, thereby forming a desired stripe partition wall.

Using an electrostatic coating machine, the fractionated body X was temporarily attached onto the glass substrate on which the indium oxide electrode was formed, and the fractionated body Y was temporarily attached onto the other glass substrate, and adjusted to a spacer so as to have an interval of 120 μm, Both glass substrates were put together, and the display apparatus which adhered the glass substrate periphery with the epoxy adhesive and enclosed the sorting body was produced. The mixing rate of the fraction X and the fraction Y was set by the same weight, and it was prepared so that the filling rate of these fractions between glass substrates may be 60 volume%. Here, the gas of the space | gap part surrounding the fractional body between board | substrates was air of 35% RH of relative humidity.

As for the display function of the obtained image display apparatus, the minimum drive voltage was 20V, the initial contrast ratio of the reflection density in black display / reflection density in white display was 9.2, and the response speed was 0.1 msec.

Moreover, the contrast ratio after 20000 times was 8.37 (keeping ratio 91%), and the contrast ratio after 5 days left was 8.19 (keeping ratio 89%).

Reference Example 22 (Second Example: Classification Object)

In Example 22, an antireflection layer formed by alternately laminating two low refractive index layers targeting silicon and two high refractive index layers targeting titanium was formed on the glass substrate.

The film of the low refractive index layer was formed using a magnetron sputtering apparatus as a sputtering apparatus, and the target gas was Si, and the supply gas was sputtered under argon 5 cc / min, oxygen gas 5 cc / min, pressure 5 mTorr, and supply power 1.2 kPa.             

The film of the high refractive index layer was formed using a magnetron sputtering apparatus as a sputtering apparatus, and the target gas was Ti, and the supply gas was sputtered under argon 5 cc / min, oxygen gas 5 cc / min, pressure 5 mTorr, and supply power 1.2 kPa.

The layer thicknesses of the low refractive index layer and the high refractive index layer were the same as in Example 1. The film forming time was 7.50 minutes for the first layer, 10.00 minutes for the second layer, 62.50 minutes for the third layer, 31.50 minutes for the fourth layer, and the total film forming time was 111.50 minutes.

In the twenty-second embodiment, the image display device of the present invention has a fast response speed and a low minimum driving voltage of 20 V, resulting in a simple structure, inexpensiveness, and excellent stability. Moreover, since a contrast ratio is high and the reflectance of visible light is very low in an antireflection layer, it turns out that a clear image is obtained.

In Example 22, the film forming time was about 2 hours, whereas in Example 22, four antireflection layers were obtained in about nine and a half, and the conductive silicon carbide was targeted at the low refractive layer, and the conductive oxidation was performed at the high refractive layer. It can be seen that by forming sputtering with titanium as a target, an antireflection layer can be formed in a very short time.

(About 4th invention)

A feature of the image display device according to the fourth aspect of the present invention is that in the image display panel having the above-described configuration, the transparent substrate 1 and the opposing substrate 2 are connected using a thermosetting adhesive or a photocuring adhesive. to be. Specifically, the adhesion of the transparent substrate 1 and the opposing substrate 2 in the image display panel 31 of the image display device of the present invention will be described in detail with reference to FIGS. 13A to 13C. .             

First, two substrates are prepared. That is, as shown to Fig.13 (a), the transparent substrate 1 in which the display electrode 3 was formed in the surface, and the opposing board | substrate 2 in which the counter electrode 4 was formed in the one surface are prepared. . The display electrode 3 is formed for each image display element 32, and a gap for providing the partition wall 7 is formed between the display electrodes 3 and 3. The counter electrode 4 is similarly formed for each image display element 32, and the partition 7 is provided upright between the counter electrodes 4 and 4. As shown in FIG.

Next, the sealing adhesive is prepared, the particles are filled, and the adhesive is applied. First, as an adhesive, a thermosetting adhesive or a photocurable adhesive, Preferably the adhesive containing one or more types of compounds which have glycidyl group, an acryl group, and methacryl group is prepared. As long as it is a thermosetting adhesive or a photocurable adhesive, any adhesive agent conventionally known can be used, but as a preferable example, 40 weight part of neopentyl glycol dimethacrylates with respect to 100 weight part of toso EVA ultracene UE750R, benzoyl peroxide The sealing adhesive which mix | blended 2 weight part is prepared. And as shown to FIG. 13 (b), the white negatively charged particle 5 and the black positively charged particle 6 are filled in the space which comprises the image display element 32 between the partitions 7. At the same time, the adhesive 33 prepared using the dispenser is applied to the four edge portions of the transparent substrate 1.

Finally, the sealing adhesive is cured by a set of two substrates and heat or light irradiation. That is, as shown to FIG. 13 (c), it sets in the state which contact | connected the transparent substrate 1 and the opposing board | substrate 2 with the adhesive agent 33 interposed, and heat or light according to the type of adhesive agent 33 Is irradiated (in the case of the adhesive agent of the composition shown as said example, it heats at 130 degreeC for 10 minutes), and the adhesive agent 33 for sealing is hardened. The image display panel 31 is obtained through the above process.

In addition, although the three image display elements 32 are formed in the cross section shown in the example shown to FIG. 13 (a)-(c), it cannot be overemphasized that the number is not limited to three. In the above-described example, the example of the image display panel having the configuration shown in FIG. 8 in which the display electrode is formed on the transparent substrate 1 and the counter electrode 4 is formed on the counter substrate 2 has been described. It is clear that the same effect can be acquired also in the image display board of the structure shown in FIG. 7 in which the display electrode 3 and the counter electrode 4 were formed in (2).

(About 5th invention)

A feature of the image display device according to the fifth aspect of the present invention is that each image display element is formed by the partition wall 7 formed between the transparent substrate 1 and the opposing substrate 2, and the shape of the partition wall 7 at that time is The bottom width wb on the opposing substrate 2 side is larger than the head width wt on the transparent substrate 1 side.

15A and 15B are longitudinal cross-sectional views each showing an example of the shape of the partition wall 7 used in the image display device of the present invention. Usually, as shown to Fig.15 (a), the cross-section trapezoid shape in which the bottom part width wb of the opposing board | substrate 2 side is larger than the head part width wt of the transparent board | substrate 1 side, More preferably, a head The ratio wt / wb of the part width wt and the bottom part width wb is set to a cross-sectional trapezoidal shape of 0.5 or less. However, as shown in FIG.15 (b), the head part width | variety (wt) is also nearly 0, and the cross section is also nearly triangular shape can also be used. When the ratio is close to 0, the head width wt is also close to 0. In this case, the effect of particle removal and the enlargement of the display area can be further enhanced, but if the ratio is excessive, the transparent substrate 1 and the partition wall 7 ) May become insufficient, and it is necessary to determine the head width w in consideration of the degree of the bonding.

By optimizing the shape of the partition wall 7 in this manner, the cross section of the partition wall 7 is rectangular, and the width of the head portion width wt of the partition wall 7 on the transparent substrate 1 side and the partition wall on the opposing substrate 2 side are determined. Compared with the conventional case where the bottom width wb is the same width, the opening ratio of the transparent substrate 1 can be increased, and the display area can be increased. Further, when the particles are filled in the space of the image display element surrounded by the partition wall 7 on the opposing substrate 2, the opening ratio of the space can be made larger than in the case of the conventional example, and the plane becomes Since the portion of the head width wt is small, there are few particles left in the portion, and the process of removing the particles from the portion of the head width wt is eliminated, so that the handling of the particles at the time of manufacturing the image display device is simplified. can do.

Specific examples of the fifth invention are shown in Figs. 14A to 16C and Fig. 16. All have the characteristics that the shape of the partition 7 was optimized. Fig. 14A shows a state in which negatively charged particles 5 and positively charged particles are arranged between opposing transparent substrate 1 and opposing substrate 2 in the reversible image display device of the present invention. In this state, when a voltage is added so that a potential difference is formed on the display electrode 3 side and the counter electrode 4 side by the power supply, as shown in Fig. 14B, both charged particles are formed by the coulomb force. 6 moves to the display electrode 3 side, and the negatively charged particles 5 move to the opposite electrode 4 side. In this case, the display surface seen from the transparent substrate 1 side is seen by the color of the positively charged particles 6. Next, when the potential of the power supply is switched and a voltage is added to the display electrode 3 and the counter electrode 4 so as to form a potential difference opposite to that described above, as shown in FIG. The negatively charged particles 5 move to the display electrode 3, and the positively charged particles 6 move to the opposite electrode 4 side. In this case, the display surface seen from the transparent substrate 1 side is seen in the color of the negatively charged particles 5.

14 (b) and 14 (c) can be repeatedly displayed by simply inverting the potential of the power source, and the color can be reversibly changed by inverting the potential of the power source. For example, when the negatively charged particles 5 are white and the positively charged particles 6 are black, or the negatively charged particles 5 are black and the positively charged particles 6 are white, The display becomes a reversible display between white and black. In the method of the present invention, since each particle is in a state of being attached to the electrode by ordinary force, the display image is maintained for a long time even after the power is turned off, and memory retention is good.

Regarding the electrode, in the example shown in FIG. 14, the display electrode 3 and the counter electrode 4, which are two kinds of electrodes having different potentials, are provided on the side facing the transparent substrate 2 of the counter substrate 2. . As another electrode arrangement method, the display electrode 3 is arrange | positioned on the transparent substrate 1, and the counter electrode 4 is arrange | positioned on the opposing board | substrate 2 like FIG. 16, but in this case, the display electrode 3 Transparent electrodes are required. In the example shown in FIG. 14, since both the display electrode 3 and the counter electrode 4 need only be an opaque electrode, inexpensive and low resistance metal electrodes, such as copper and aluminum, can be used. The external voltage may be superimposed on direct current or alternating current. It is preferable that each electrode forms an insulating coat layer so that the charge of charged particles does not escape. This coat layer is particularly preferable because the use of positively charged resin for negatively charged particles and negatively charged resin for positively charged particles makes it difficult for the charge of the particles to escape.

In addition, the above-described example is the same even if a fraction is used instead of the particle.

Next, an Example and a comparative example are shown and 5th invention of this invention is demonstrated more concretely. However, the present invention is not limited by the following examples.

<Example of the fifth invention>

Example 41 (First Example: Particles)

As shown in FIG. 17, after laminating | stacking the polycarbonate 41 on the opposing board | substrate 2, the mold was transferred by the mold 42, and the partition structure was formed. The bottom width of the partition 7 was larger than the head width. After the particles 5, 6 are filled by the partition structure by the scattering method, when joining the transparent substrate 1, it is necessary to remove unnecessary particles from the tip of the partition wall 7, on the partition wall 7 In the present structure having a narrow area, the particles 5 and 6 could be easily removed. After particle removal, the positions of the transparent substrate 1 and the counter substrate 2 are determined, and a sealing material is applied between the transparent substrate 1 and the partition wall 7 to bond the transparent substrate 1 and the partition wall 7 to each other. It was. As a result, an image display device with a large display area and good adhesion between the partition wall 7 and the transparent substrate 1 was obtained.

Example 42 (First Example: Particles)

As shown in FIG. 18, the mold 42 was pushed to the opposing board | substrate 2, and UV curable acrylic resin was poured. UV was irradiated 100OmJ / cm <2> at the side of the opposing board | substrate 2 (glass substrate), and resin was hardened and the partition structure was formed. The bottom width of the partition 7 was larger than that of Example 41 than the head width. After the particles 5, 6 are filled in the partition structure by the scattering method, when bonding the transparent substrate 1, it is necessary to remove unnecessary particles from the tip of the partition wall 7, but the area on the partition wall 7 In this very narrow present structure, it was not necessary to remove the particles 5 and 6. After the particles are filled in the barrier rib structure, the positions of the transparent substrate 1 and the counter substrate 2 are determined, and a sealing material is applied between the transparent substrate 1 and the barrier rib 7 to form the transparent substrate 1 and the barrier rib ( 7) was bonded. As a result, an image display device having a very large display area and excellent adhesion to the partition wall 7 and the transparent substrate 1 to some extent was obtained.

Comparative Example 41 (First Example: Particles)

As shown in FIG. 19, the partition structure was formed in the exposure and image development process by the photolithographic method. After the particles 5, 6 are filled by the scattering method in the partition structure, when the transparent substrate 1 is attached, it is necessary to remove unnecessary particles from the tip of the partition wall 7. In the present structure, the partition wall 7 ) The area of the phase is large, it is necessary to sufficiently remove the particles, there is a problem that the process is complicated.             

Next, as an example of the second embodiment of the fifth invention, an example using a classifier was examined.

Example 43 (Second Example: Sort)

As shown in FIG. 17, after laminating | stacking the polycarbonate 41 on the opposing board | substrate 2, the mold was transferred by the mold 42, and the partition structure was formed. The bottom width of the partition 7 was larger than the head width. After filling the classifiers 5 and 6 with the partition structure by the scattering method, when joining the transparent substrate 1, it is necessary to remove the unnecessary classifier from the tip of the partition wall 7, but the partition wall 7 In the present structure having a narrow area of), the fractions 5 and 6 could be easily removed. After removing the separator, the transparent substrate 1 and the counter substrate 2 are positioned, the sealing material is applied between the transparent substrate 1 and the partition wall 7 to bond the transparent substrate 1 and the partition wall 7 to each other. It was. As a result, an image display device with a somewhat large display area and good adhesion between the partition wall 7 and the transparent substrate 1 could be obtained.

Example 44 (Second Example: Sort)

As shown in FIG. 18, the mold 42 was pushed to the opposing board | substrate 2, and UV curable acrylic resin was poured. UV was irradiated 1000mJ / cm <2> at the side of the opposing board | substrate 2 (glass substrate), and resin was hardened and the partition structure was formed. The bottom width of the partition 7 was larger than that of Example 43 than the head width. After filling the classifiers 5 and 6 with the partition structure by the scattering method, when attaching the transparent substrate 1, it is necessary to remove the unnecessary classifiers from the tip of the partition wall 7, but the partition wall 7 In this structure where the phase area was very narrow, it was not necessary to remove the fractions 5 and 6. After filling the partition with the partition structure, the transparent substrate 1 and the counter substrate 2 are positioned, and a sealing material is applied between the transparent substrate 1 and the partition wall 7 to form the transparent substrate 1 and the partition wall ( 7) was attached. As a result, an image display device having a very large display area and excellent adhesion to the partition wall 7 and the transparent substrate 1 to some extent was obtained.

Comparative Example 42 (Second Example: Sort)

As shown in FIG. 19, the partition structure was formed in the exposure and image development process by the photolithographic method. After filling the partitions 5 and 6 with the partition structure by the scattering method, when attaching the transparent substrate 1, it is necessary to remove unnecessary fractions from the distal end of the partition wall 7. The area of (7) phase was large, it was necessary to fully remove a fraction, and there existed a problem that a process became complicated.

(About 6th invention)

A feature of the manufacturing method of the image display device according to the sixth invention of the present invention lies in that the manufacturing method of the partition wall 7 forming the image display element is improved in manufacturing the image display device having the above-described configuration. That is, as shown in FIG. 20, the adhesive agent 51 is formed in the front-end | tip of the partition 7 formed on the opposing board | substrate 2, and the partition 7 and the transparent substrate 1 are fixed through the adhesive 51. As shown in FIG. Thus, an image display element is formed by the partition wall 7 between the transparent substrate 1 and the opposing substrate 2, or as shown in FIG. 21, the partition wall is formed in both the transparent substrate 1 and the opposing substrate 2. (7-1, 7-2) are formed, the front end of one partition here, the adhesive agent 51 is formed in the front end of the partition 7-1, and the partitions 7-1 and 7-2 are adhesive agent 51 It is fixed through and the image display element is formed by the partition wall 7 between the transparent substrate 1 and the opposing substrate 2. In addition, in the example shown in FIG. 20 and FIG. 21, in order to simplify description, the negatively charged particle 5, the positively charged particle 6, and the electrodes 3 and 4 are abbreviate | omitted and demonstrated, In fact, these members Is present. The classification is also the same.

By forming the partition wall 7 in this way, the partition wall 7 can be firmly formed between the transparent substrate 1 and the opposing board | substrate 2, and the outflow of particle was suppressed in the space which comprises an image display element. A predetermined amount of particles can be completely enclosed in a state.

Next, an Example and a comparative example are shown and 6th invention of this invention is demonstrated more concretely. However, the present invention is not limited by the following examples.

<Example of Sixth Invention>

Example 51 (First Example: Particles)

As shown in FIG. 22, the partition 7 is arrange | positioned on the opposing board | substrate 2, and the negatively charged particle 5 and the positively charged particle (in the space which comprise the image display element formed between the partitions 7) 6) was charged. In that state, the thermosetting adhesive 52 is screen printed on the tip of the partition 7, the transparent substrate 1 is positioned relative to the counter substrate 2, and heated at 100 ° C. × 20 minutes × 0.1 MPa. It pressurized and the partition 7 and the transparent substrate 1 were bonded together through the adhesive agent 52. As the thermosetting adhesive 12, a radically polymerizable adhesive containing an organic peroxide was used. And the display characteristic after repeating initial characteristic and 50 million display was calculated | required and evaluated. The evaluation method used the optical density meter and computed the difference of the maximum OD value and the minimum OD value as a contrast ratio when the voltage was applied to the image display apparatus. The results are shown in Table 4 below.

Example 52 (First Example: Particles)

As shown in FIG. 23, the partition 7 is arrange | positioned on the opposing board | substrate 2, and the negatively charged particle 5 and the positively charged particle (in the space which comprise the image display element formed between the partitions 7) 6) was charged. In that state, the UV curable adhesive 53 is laminated on the whole surface which opposes the opposing board | substrate 2 of the transparent board | substrate 1, the transparent board | substrate 1 is positioned with respect to the opposing board | substrate 2, and 1000mJ / UV of cm2 was irradiated, and the partition 7 and the transparent substrate 1 were bonded together through the adhesive 53. And the display characteristic after repeating initial characteristic and 50 million times of display was calculated | required, and it evaluated like Example 51. The results are shown in Table 4 below.

Comparative Example 51 (Example 1: Particles)

As shown in FIG. 24, the partition 7 is arrange | positioned on the opposing board | substrate 2, and the negatively charged particle 5 and the positively charged particle 6 are comprised in the space which comprises the image display element formed in the partition 7. ) Was charged. In this state, the transparent substrate 1 and the opposing substrate 2 are laminated by only positioning the transparent substrate 1 and the opposing substrate 2 without applying the adhesive to the partition 7, and the transparent substrate. The sealing agent was formed and joined to the corner part of (1) and the partition 7. And the display characteristic after repeating initial characteristic and 50 million times of display was calculated | required, and it evaluated like Example 51. The results are shown in Table 4 below.

Table 4

Initial display properties Display characteristics after 50 million displays Example 51 15 13 Example 52 13 12 Comparative Example 51 14 3

From the results of Table 4, in Examples 51 and 52 according to the manufacturing method of the present invention, contrast deterioration was hardly observed even after 50 million displays, whereas in Comparative Example 51 according to the conventional manufacturing method, particles were interposed between the image display elements. Remarkable display deterioration was observed because of the shift.

Next, as an example of the second embodiment of the sixth invention, an example using a classifier was examined.

Example 53 (Second Example: Sort)

As shown in FIG. 22, the partition 7 is arrange | positioned on the opposing board | substrate 2, and the negative charge sorting body 5 and the positive charge sorting are in the space which comprises the image display element formed between the partitions 7. Sieve 6 was filled. In that state, the thermosetting adhesive 52 is screen printed on the front end of the partition wall 7, the transparent substrate 1 is positioned with respect to the opposing substrate 2, and heated and pressurized at 100 ° C. × 20 minutes × 0.1 MPa. The partition 7 and the transparent substrate 1 were bonded together via the adhesive 52. As the thermosetting adhesive 52, a radically polymerizable adhesive containing an organic peroxide was used. And the display characteristic after repeating initial characteristic and 50 million display was calculated | required and evaluated. The evaluation method used the optical density meter and computed the difference of the maximum OD value and the minimum OD value as a contrast ratio when the voltage was applied to the image display apparatus. The results are shown in Table 5 below.

Example 54 (Second Example: Sort)

As shown in FIG. 23, the partition 7 is arrange | positioned on the opposing board | substrate 2, and the negative charge sorting body 5 and the positive charge sorting are in the space which comprises the image display element formed between the partitions 7. Sieve 6 was filled. In that state, the UV curable adhesive 53 is laminated on the whole surface which opposes the opposing board | substrate 2 of the transparent board | substrate 1, the transparent board | substrate 1 is positioned with respect to the opposing board | substrate 2, and 1000mJ / UV of cm2 was irradiated, and the partition 7 and the transparent substrate 1 were bonded together through the adhesive 53. And the display characteristic after repeating initial characteristic and 50 million times of display was calculated | required, and it evaluated like Example 53. The results are shown in Table 5 below.

Comparative Example 52 (Second Example: Sort)

As shown in FIG. 24, the partition 7 is arrange | positioned on the opposing board | substrate 2, and the negatively charged classifier 5 and the positively charged classifier are in the space which comprises the image display element formed in the partition 7. (6) was charged. In this state, only the positions of the transparent substrate 1 and the opposing substrate 2 are determined without laminating an adhesive to the partition 7, and the transparent substrate 1 and the opposing substrate 2 are laminated, and the transparent substrate ( 1) and the sealing compound were formed in the corner part of the partition 7, and were joined. And the display characteristic after repeating initial characteristic and 50 million times of display was calculated | required, and it evaluated like Example 53. The results are shown in Table 5 below.             

Table 5

Initial display properties Display characteristics after 50 million displays Example 53 16 14 Example 54 15 13 Comparative Example 52 15 3

From the results of Table 5, in Examples 53 and 54 according to the manufacturing method of the present invention, contrast deterioration was hardly observed even after 50 million displays, whereas in Comparative Example 52 according to the conventional manufacturing method, particles were interposed between the image display elements. Remarkable display deterioration was observed because of the shift.

Industrial availability

As can be seen from the above description, according to the image display device according to the first aspect of the present invention, a signal for printing a circuit for displaying an image at the same time having a fast response speed, a simple structure, a low cost, and excellent stability. By using an anisotropic conductive film for connecting a member such as an electrode to a substrate and a substrate, the member such as an electrode can be mounted on the substrate at a low temperature for a short time, and the adverse effect on the substrate when mounting the electrode is minimized. It can suppress and can manufacture the image display apparatus of the outstanding performance efficiently.

Further, according to the image display device according to the second invention of the present invention, the response speed is fast, the simple structure, the cost is excellent, the stability is excellent, and the image display panel is integrated through the optical function member and the transparent elastic layer, thereby achieving a contrast ratio. Deterioration, deformation of a display screen, color unevenness, etc. can be prevented reliably, and a clear image is obtained.             

Moreover, according to the image display apparatus which concerns on the 3rd invention of this invention, since a response speed is fast, it is simple structure, it is cheap, it is excellent in stability, and external light reflection is suppressed, a contrast is high and a clear image is obtained. .

In addition, by forming sputtering with conductive silicon carbide as a target in the low refractive index layer and conductive titanium oxide as a target in the high refractive layer, the antireflection film can be formed in a very short time, and the antireflection film having excellent productivity can be easily formed. Can be made.

Moreover, according to the image display apparatus which concerns on 4th invention of this invention, since two board | substrates, specifically, a transparent board | substrate and an opposing board | substrate are connected using a thermosetting adhesive or a photocuring adhesive, 2 After setting the enteric substrate at a predetermined position, the adhesive can be cured in a short time by irradiating heat or light to prevent misalignment between the substrates and leakage of particles or fractions. Thereby, the high image display precision of an image display board can be realized.

Moreover, according to the image display apparatus which concerns on the 5th invention of this invention, the shape of a partition is made to contact a transparent substrate by making the bottom width wb of the opposing board | substrate side larger than the head width wt of the transparent board | substrate side. The portion of the partition wall can be reduced, the display area can be increased, and the particles or fraction remaining in the head portion of the partition wall can be reduced when the particles or fractions are filled inside the image display element surrounded by the partition walls. Therefore, the handling of the particles or the fraction at the time of manufacture can be simplified.

Moreover, according to the manufacturing method of the image display apparatus which concerns on the 6th invention of this invention, a partition is formed in one or both of a transparent board | substrate and an opposing board | substrate, an adhesive agent is formed in the front-end | tip of a partition, and the other board | substrate or partition is partitioned. By bonding them together with an adhesive, it is possible to firmly use the bonding between the partition walls and the substrate, or the joining of the partition walls, and to prevent the harmful effects of moving the particles or the fractions over the partition walls, thereby almost completely sealing the particles or the fractions. have.

Claims (46)

delete delete delete delete An image display panel for encapsulating one or more types of particle groups between two opposing substrates at least one of which is transparent, and providing an electric field to the particle groups at two kinds of electrodes having different potentials to move the particles to display an image, and an optical function A member, the image display panel and the optical function member are integrated with a transparent elastic layer interposed therebetween, When the refractive index of the transparent elastic layer is n ₀ , the refractive index of the optical function member is n ₁ , and the refractive index of the transparent substrate of the image display panel is n ₂ , the absolute value of the difference between n ₀ and n ₁ and n ₀ And an absolute value of the difference between n and n ₂ is 0.2 or less, respectively. delete The method of claim 5, When the transparent elastic layer made the strain (ε ₀ ) at 25 ° C., a stress relaxation characteristic, 5% and the initial value of the stress relaxation modulus (after 0.05 seconds) to G ₀ , G ₀ was 6.5 × 10 ⁶ Pa The relationship between the stress relaxation modulus (G) and the time (t (seconds)) obtained from the damping curve of the stress relaxation modulus, lnG (t) = -t / τ + lnG ₀ The image display apparatus whose stress relaxation time (tau) computed by is 17 second or less. An image display apparatus in which at least one type of particle group is enclosed between two opposing substrates, and two types of electrodes having different potentials are used to impart an electric field to the particle group to move the particles to display an image. An anti-reflection layer made of a plurality of layers having different refractive indices is formed on the surface of the transparent substrate. The method of claim 8, An antireflection layer is formed by stacking a low refractive index layer formed by sputtering using conductive silicon carbide as a target and a high refractive layer formed by sputtering using conductive titanium oxide as a target. The method according to claim 8 or 9, An image display apparatus in which the antireflection layer prevents reflection of light having a wavelength of 380 to 780 nm and has a light reflectance of 10% or less. delete delete Two or more types of particle groups having different colors and charging characteristics are enclosed between at least two opposing substrates which are transparent, and an electric field is applied to the particle groups by two kinds of electrodes having different dislocations to move the particles to display an image. An image display device having an image display panel, comprising one or more image display elements separated from each other by partition walls, and the shape of the partition walls is such that the bottom width wb on the opposite substrate side is the width of the head portion on the transparent substrate side. (wt) larger than the image display device. The method of claim 13, The ratio (wt / wb) of the bottom width (wb) of the counter substrate side to the width of the head (wt) of the transparent substrate side is 0.5 or less. The method according to claim 13 or 14, An image display apparatus in which the particle group color is white and black. The method according to any one of claims 5, 8 and 13, An image display apparatus in which the average particle diameter of the particles is 0.1 to 50 µm. The method according to any one of claims 5, 8 and 13, The image display apparatus whose absolute value of the difference of surface charge density of the two types of particle | grains measured by the blow-off method using the same kind of carrier is 5 microC / m <2> -150 microC / m <2>. When the particles were charged with a voltage of 8 kV to generate a corona discharge to a corona discharger disposed at a distance of 1 mm from the surface, the maximum value of the surface potential after 0.3 second was greater than 300 V. The manufacturing method of the image display apparatus in any one of Claim 5, 7-9, 13, 14 which are particle | grains. delete delete delete delete delete delete As an image display device between at least one of the two opposing substrates, a sorting body exhibiting high fluidity is enclosed in an aerosol state in which a solid substance stably floats as a dispersoid in a gas, and moves the sorting body. And a member which sends a signal applied to the circuit of an image display to a board | substrate with an anisotropic conductive film, The image display apparatus characterized by the above-mentioned. The method of claim 25, The anisotropic conductive film disperse | distributes electroconductive particle in a thermosetting adhesive or a photocurable adhesive agent, The image display apparatus. The method of claim 26, The image display apparatus whose diameter of the electroconductive particle disperse | distributed in a thermosetting adhesive or a photocurable adhesive agent is 0.1-20 micrometers. The method of claim 26 or 27, An image display apparatus in which the thermosetting adhesive or the photocurable adhesive contains at least one kind of a compound having any one of glycidyl group, acryl group and methacryl group. An image display panel and a optical function member for enclosing a sorting body exhibiting high fluidity in an aerosol state in which a solid substance stably floats as a dispersoid in a gas between at least one of the two opposing substrates which are transparent. And an image display plate and an optical function member are integrated with a transparent elastic layer interposed therebetween. The method of claim 29, When the refractive index of the transparent elastic layer is n ₀ , the refractive index of the optical function member is n ₁ , and the refractive index of the transparent substrate of the image display panel is n ₂ , the absolute value of the difference between n ₀ and n ₁ and n ₀ And an absolute value of the difference between n and n ₂ , respectively, equal to or less than 0.2. The method of claim 29 or 30, When the transparent elastic layer has a strain (ε ₀ ) at 25 ° C., which is a stress relaxation property, as 5%, and an initial value (after 0.05 seconds) of the stress relaxation modulus as G ₀ , G ₀ is 6.5 × 10 ⁶ Pa The relationship between the stress relaxation modulus (G) and the time (t (seconds)) obtained from the damping curve of the stress relaxation modulus, lnG (t) = -t / τ + lnG ₀ The image display apparatus whose stress relaxation time (tau) computed by is 17 second or less. An image display device for filling a separator having high fluidity in an aerosol state in which a solid substance stably floats as a dispersoid in a gas between at least one of the two opposing substrates, and moving the separator. An anti-reflection layer comprising a plurality of layers having different refractive indices is formed on a surface thereof. The method of claim 32, An antireflection layer is formed by stacking a low refractive index layer formed by sputtering using conductive silicon carbide as a target and a high refractive layer formed by sputtering using conductive titanium oxide as a target. 34. The method of claim 32 or 33, An image display apparatus in which the antireflection layer prevents reflection of light having a wavelength of 380 to 780 nm and has a light reflectance of 10% or less. An electrode comprising an electrode formed on one or both sides of a substrate between a two opposing substrates at least one of which is filled with a fractionating body exhibiting high fluidity in an aerosol state in which a solid substance stably floats as a dispersoid in a gas. An image display device comprising an image display panel for applying an electric field to the classifier in a pair and moving the classifier to display an image, wherein the two substrates of the image display panel are connected using a thermosetting adhesive or a photocuring adhesive. An image display device, characterized by the above-mentioned. 36. The method of claim 35 wherein The image display apparatus in which the said thermosetting adhesive or photocurable adhesive contains one or more types of compounds which have glycidyl group, an acryl group, and a methacryl group. Between two opposing substrates at least one of which is transparent, a classifying body having a high fluidity is enclosed in an aerosol state in which a solid substance stably floats as a dispersoid in a gas, and an electrode pair composed of electrodes having different potentials is applied to the classifying body. An image display device comprising an image display plate for applying an electric field to move the sorting body to display an image, having one or more image display elements isolated from each other by a partition wall, and having a shape of the partition wall on the opposite substrate side. An bottom display width (wb) is larger than a head width (wt) on the transparent substrate side. The method of claim 37, The ratio (wt / wb) of the bottom width (wb) of the counter substrate side to the width of the head (wt) of the transparent substrate side is 0.5 or less. The method according to any one of claims 25, 29, 32, 35, 37, An image display device in which the appearance volume at the time of maximum floating of the fractional body is twice or more than that at the time of non-floating. The method according to any one of claims 25, 29, 32, 35, 37, The time change of the appearance volume of the classification body, V ₁₀ / V ₅ > 0.8 The image display device that satisfies. (V ₅ represents the apparent volume (cm 3) of the fraction after 5 minutes from the maximum suspension, and V ₁₀ represents the apparent volume (cm 3) of the fraction after 10 minutes from the maximum suspension.) The method according to any one of claims 25, 29, 32, 35, 37, The image display apparatus whose average particle diameter (d (0.5)) of a classification body is 0.1-20 micrometers. Between two opposing substrates at least one of which is transparent, a classifying body having a high fluidity is enclosed in an aerosol state in which a solid substance stably floats as a dispersoid in a gas, and an electrode pair composed of electrodes having different potentials is applied to the classifying body. A manufacturing method of an image display apparatus having an image display plate having one or more image display elements separated from each other by partition walls by applying an electric field to move the sorting body, wherein one of the transparent substrate and the opposing substrate is provided. Or a partition is formed in both sides, the adhesive agent is formed in the front-end | tip of a partition, and the partition and the other board | substrate or partitions were bonded together through the adhesive, The manufacturing method of the image display apparatus characterized by the above-mentioned. The method of claim 42, The manufacturing method of the image display apparatus which is 2 times or more of the external appearance volume at the time of the maximum floating of a classification body. 44. The method of claim 42 or 43, wherein the change in time of the apparent volume of the fraction is V ₁₀ / V ₅ > 0.8 The manufacturing method of the image display apparatus which satisfy | fills. (V ₅ represents the apparent volume (cm 3) of the fraction after 5 minutes from the maximum suspension, and V ₁₀ represents the apparent volume (cm 3) of the fraction after 10 minutes from the maximum suspension.) The method of claim 42 or 43, The manufacturing method of the image display apparatus whose average particle diameter (d (0.5)) of the particle | grains which comprise a classification body is 0.1-20 micrometers. The image display apparatus manufactured by the manufacturing method of the image display apparatus of Claim 42 or 43.

Images